EP2243987B1 - Dichtungskörper mit kugelförmiger zone und verfahren zu seiner herstellung - Google Patents

Dichtungskörper mit kugelförmiger zone und verfahren zu seiner herstellung Download PDF

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Publication number
EP2243987B1
EP2243987B1 EP08861908.5A EP08861908A EP2243987B1 EP 2243987 B1 EP2243987 B1 EP 2243987B1 EP 08861908 A EP08861908 A EP 08861908A EP 2243987 B1 EP2243987 B1 EP 2243987B1
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EP
European Patent Office
Prior art keywords
outer layer
heat
resistant material
reinforcing member
spherical annular
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EP08861908.5A
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English (en)
French (fr)
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EP2243987A4 (de
EP2243987A1 (de
Inventor
Shuichi Kubota
Koichi Ishida
Satoshi Matsunaga
Eiji Satou
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Oiles Corp
Oiles Industry Co Ltd
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Oiles Corp
Oiles Industry Co Ltd
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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16J—PISTONS; CYLINDERS; SEALINGS
    • F16J15/00—Sealings
    • F16J15/02—Sealings between relatively-stationary surfaces
    • F16J15/06—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces
    • F16J15/10—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing
    • F16J15/12—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing with metal reinforcement or covering
    • F16J15/121—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing with metal reinforcement or covering with metal reinforcement
    • F16J15/126—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing with metal reinforcement or covering with metal reinforcement consisting of additions, e.g. metallic fibres, metallic powders, randomly dispersed in the packing
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N13/00—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00
    • F01N13/18—Construction facilitating manufacture, assembly, or disassembly
    • F01N13/1805—Fixing exhaust manifolds, exhaust pipes or pipe sections to each other, to engine or to vehicle body
    • F01N13/1827—Sealings specially adapted for exhaust systems
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L27/00—Adjustable joints, Joints allowing movement
    • F16L27/02—Universal joints, i.e. with mechanical connection allowing angular movement or adjustment of the axes of the parts in any direction
    • F16L27/04—Universal joints, i.e. with mechanical connection allowing angular movement or adjustment of the axes of the parts in any direction with partly spherical engaging surfaces
    • F16L27/06—Universal joints, i.e. with mechanical connection allowing angular movement or adjustment of the axes of the parts in any direction with partly spherical engaging surfaces with special sealing means between the engaging surfaces
    • F16L27/073—Universal joints, i.e. with mechanical connection allowing angular movement or adjustment of the axes of the parts in any direction with partly spherical engaging surfaces with special sealing means between the engaging surfaces one of the cooperating surfaces forming the sealing means
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2530/00—Selection of materials for tubes, chambers or housings
    • F01N2530/18—Plastics material, e.g. polyester resin
    • F01N2530/20—Plastics material, e.g. polyester resin reinforced with mineral or metallic fibres

Definitions

  • the present invention relates to a spherical annular seal member used in a spherical pipe joint for an automobile exhaust pipe, as well as a method of manufacturing the same.
  • JP 2006-322601A discloses a spherical annular seal member in accordance with the pre-characterizing section of claim 1.
  • JP 2004-044735A discloses a spherical zone seal body comprising: a through hole at a central section; a spherical zone substrate that is prescribed by a cylindrical inner surface, a partial convex surface, and annular end faces in the large-diameter and small-diameter sides of the partial convex surface; and an outer layer that is integrated with the partial convex surface in the spherical zone substrate.
  • an exhaust system incorporating an exhaust emission control device such as a catalyzer is adopted to purify exhaust gases emitted from the vehicle.
  • exhaust gases from the automobile engine are generally led to an exhaust manifold 500 and are released from a tail pipe 505 into the atmosphere through a catalytic converter 501, an exhaust pipe 502, a prechamber 503, and a silencer 504.
  • the exhaust emission control device in the above-described exhaust system is a heavy object.
  • the exhaust emission control device constitutes the mass of a vibrating system and can be a factor causing the problem of noise and the like, to absorb the vibrations of this exhaust system
  • means are adopted by disposing a flexible joint, for instance, a spherical pipe joint at a required portion of the exhaust system so as to absorb the vibrations.
  • the seal member used in the spherical pipe joint described in the patent document 1 has advantages in that it is heat resistant, excels in affinity with a mating member, and its impact strength is remarkably improved.
  • the seal member has a drawback in that it often generates abnormal frictional noise when it undergoes sliding friction under dry frictional conditions.
  • each of these seal members 600 is comprised of a spherical annular base member 605 defined by a cylindrical inner surface 601, a partially convex spherical surface 602, and large- and small-diameter-side annular end faces 603 and 604 of the partially convex spherical surface 602, as well as an outer layer 606 formed integrally on the partially convex spherical surface 602 of the spherical annular base member 605.
  • the spherical annular base member 605 includes a reinforcing member 607 made from a metal wire net and a heat-resistant material 608 containing expanded graphite, filling meshes of the metal wire net of the reinforcing member 607, and compressed in such a manner as to be formed integrally with the reinforcing member 607 in mixed form.
  • a lubricant 609 and a heat-resistant material 610 as well as a reinforcing member 611 made from a metal wire net are compressed such that the lubricant 609 and the heat-resistant material 610 are filled in meshes of the metal wire net of the reinforcing member 611, and the lubricant 609 and the heat-resistant material 610 as well as the reinforcing member 611 are integrally formed in mixed form.
  • An outer surface 612 of the outer layer 606 is formed into a smooth surface in which a surface 613 constituted of the reinforcing member 611 and a surface 614 constituted of the lubricant 609 are present in mixed form.
  • the outer surface 612 of the outer layer 606 of the above-described seal member 600 is formed into a smooth surface in which the surface 613 constituted of the reinforcing member 611 and the surface 614 constituted of the lubricant 609 are present in mixed form, it is possible to ensure smooth sliding with a concave spherical portion of the exhaust pipe, i.e., the mating member which is in sliding contact with the outer surface 612.
  • the transfer of the lubricant 609 from the outer surface 612 onto the surface of the concave spherical portion is effected to form on the concave spherical portion a lubricating film constituted of the lubricant 609.
  • the reinforcing member 611 exposed on the outer surface 612 in a scattered manner demonstrates scraping action while leaving an appropriate amount of the lubricating film.
  • the present inventors discovered organic relationships between the heat-resistant material and the reinforcing member, including the proportion of exposure of the reinforcing member made from the metal wire net in the outer layer of the seal member, the degree of adherence between the reinforcing member and the heat-resistant material constituted of expanded graphite, and the wire diameter of the fine metal wire for forming the metal wire net of the reinforcing member.
  • the present inventors obtained knowledge that the above-described problems can be overcome by improving these relationships.
  • the present invention has been devised on the basis of the above-described knowledge, and its object is to provide a spherical annular seal member which is capable of preventing as much as possible the damaging and coarsening of the surface of the mating member in the sliding friction with the mating member, and of preventing as much as possible the decline in sealability and the generation of abnormal frictional noise, as well as a method of manufacturing the same.
  • a spherical annular seal member for use in an exhaust pipe joint in accordance with the present invention comprises: a spherical annular base member defined by a cylindrical inner surface, a partially convex spherical surface, and large- and small-diameter-side annular end faces of the partially convex spherical surface; and an outer layer formed integrally on the partially convex spherical surface of said spherical annular base member, wherein said spherical annular base member includes a reinforcing member made from a metal wire net and a heat-resistant material containing expanded graphite, filling meshes of said metal wire net of said reinforcing member, and compressed in such a manner as to be formed integrally with said reinforcing member in mixed form, and wherein said outer layer includes a base layer and a sliding layer constituted of a lubricating composition and adherently formed integrally on said base layer at an outer layer intermediate surface, said base layer including another reinforc
  • the surface of the other reinforcing member in the outer layer intermediate surface of the base layer is present in a scattered manner with an area ratio of 5 to 35% with respect the entire surface of the outer layer intermediate surface, a sliding layer constituted of a lubricating composition is adherently formed integrally on the outer layer intermediate surface, and the obverse surface of the outer layer exposed to the outside is constituted of a smooth surface of the sliding layer. Therefore, in the friction with the mating member, it is possible to avoid only the other reinforcing member of the outer layer from locally rubbing against the surface of the mating member.
  • the heat-resistant materials of the spherical annular base member and the outer layer contain expanded graphite and at least one of 0.05 to 5.00 wt.% of phosphorus pentoxide as an oxidation inhibitor and 1.0 to 16.0 wt.% of a phosphate as an oxidation inhibitor.
  • the heat-resistant materials which contain expanded graphite and at least one of phosphorus pentoxide as an oxidation inhibitor and a phosphate as an oxidation inhibitor are capable of improving the heat resistance and oxidation loss resistance of the spherical annular seal member itself, and permit the use of the spherical annular seal member over extended periods of time at 500°C or in a high-temperature range exceeding 500°C.
  • the metal wire nets of the reinforcing members of the spherical annular base member and the outer layer are made from woven metal wire nets and braided metal wire nets obtained by, for instance, weaving or knitting fme metal wires.
  • the fine metal wires for forming the woven metal wire net and the braided metal wire net fine metal wires whose wire diameters are in the range of 0.15 to 0.32 mm, more specifically fine metal wires whose wire diameters are 0.15, 0.175, 0.28, and 0.32 mm, are suitable.
  • metal wire nets of the reinforcing members of the spherical annular base member and the outer layer woven metal wire nets and braided metal wire nets made from fine metal wires of the same wire diameter may be used.
  • a woven metal wire net and a braided metal wire net made from a fine metal wire having a wire diameter of the upper limit side of the aforementioned range, i.e., 0.28 to 0.32 mm may be used
  • metal wire net of the reinforcing member for an outer layer a woven metal wire net or a braided metal wire net made from a fine metal wire having a wire diameter of the lower limit side of the aforementioned range, i.e., 0.15 to 0.175 mm, may be used.
  • the lubricating composition of the sliding layer formed on the outer layer intermediate surface in a preferred example is constituted of a simple substance of a polytetrafluoroethylene resin or contains a polytetrafluoroethylene resin.
  • the lubricating composition contains 70 to 85 wt.% of hexagonal boron nitride, 0.1 to 10 wt.% of boron oxide, and 5 to 20 wt.% of hydrated alumina.
  • the lubricating composition containing 70 to 85 wt.% of hexagonal boron nitride, 0.1 to 10 wt.% of boron oxide, and 5 to 20 wt.% of hydrated alumina not more than 300 parts by weight or not more than 200 parts by weight, preferably 50 to 200 parts by weight or 50 to 150 parts by weight, of the polytetrafluoroethylene resin is contained with respect to 100 parts by weight of the lubricating composition.
  • Such a lubricating composition may be selected by being appropriately selected in accordance with the intended use.
  • the sliding layer constituted of such a lubricating composition forms a smooth surface as the sliding surface of the spherical annular seal member, and such a flat surface makes it possible to effect smooth sliding without generating abnormal frictional noise in the sliding with the mating member.
  • the hydrated alumina in the above lubricating composition in a preferred example is selected from alumina monohydrate such as boehmite or diaspore, alumina trihydrate such as gibbsite or bayerite, and pseudoboehmite.
  • the present invention provides a method of manufacturing the spherical annular seal member in accordance with the invention, which is used in an exhaust pipe joint and includes a spherical annular base member defined by a cylindrical inner surface, a partially convex spherical surface, and large- and small-diameter-side annular end faces of the partially convex spherical surface, and an outer layer formed integrally on the partially convex spherical surface of said spherical annular base member, the method characterized by comprising the steps of: (a) preparing a heat-resistant material for the spherical annular base member constituted of an expanded graphite sheet with a density of ⁇ Mg/m 3 ; (b) preparing a reinforcing member for the spherical annular base member made from a metal wire net obtained by weaving or knitting fine metal wires, superposing said reinforcing member for the spherical annular base member on said heat-resistant material for the
  • the heat-resistant material for the outer layer constituted of expanded graphite sheet having a lower density than the density of the expanded graphite sheet forming the heat-resistant material for the spherical annular base member is inserted into two layers of the reinforcing member for the outer layer made from the metal wire net, and the reinforcing member for the outer layer with such a heat-resistant material for the outer layer inserted therein is pressurized in the thicknesswise direction of the heat-resistant material and is thereby press bonded to each other, such that the heat-resistant material for the outer layer is densely filled in the meshes of the metal wire net of the reinforcing member for the outer layer, and the reinforcing member for the outer layer is embedded in the heat-resistant material for the outer layer.
  • the reinforcing member is present in a scattered manner in its outer layer intermediate surface with the area ratio of 5 to 35%. Therefore, in the friction with the mating member, it is possible to avoid only the reinforcing member of the outer layer from locally rubbing against the surface of the mating member. As a result, it is possible to prevent the damaging and coarsening of the surface of the mating member as much as possible due to friction, so that it is possible to prevent a decline in sealability.
  • a method of pressurization is suitably used in which the pressurization, in the thicknesswise direction of the heat-resistant sheet member, of the reinforcing member for the outer layer with the heat-resistant sheet member for the outer layer inserted therein is effected, for example, by feeding the same into a nip between a cylindrical roller having a smooth outer peripheral surface and a roller having a cylindrical outer peripheral surface with a plurality of annular recessed grooves provided along the axial direction, and subsequently by further feeding the same into a nip between another pair of cylindrical rollers each having a smooth cylindrical outer peripheral surface.
  • a method of pressurization is suitably used in which the pressurization, in the thicknesswise direction of the heat-resistant sheet member, of the reinforcing member for the outer layer with the heat-resistant sheet member for the outer layer inserted therein is effected, for example, by feeding the same into a nip between at least a pair of cylindrical rollers each having a smooth cylindrical outer peripheral surface.
  • the density ⁇ of the heat-resistant material for the spherical annular base member is 1.0 to 1.5 Mg/m 3 , preferably 1.0 to 1.2 Mg/m 3
  • the density of the heat-resistant material for the outer layer is 0.3- to 0.6-fold the density of the heat-resistant material for the spherical annular base member, i.e., 0.3 to 0.9 Mg/m 3 , preferably 0.3 to 0.6 Mg/m 3 .
  • the surface roughness of the flat composite sheet member obtained in the aforementioned step (c) is, in a preferred example, 5 to 30 ⁇ m in an arithmetic average roughness Ra.
  • the reinforcing member for the outer layer is present in a scattered manner in the outer layer intermediate surface of the outer layer with an area ratio of 5 to 35%, and the surface roughness of the outer layer intermediate surface of the outer layer is 5 to 30 ⁇ m in the arithmetic average roughness Ra.
  • the heat-resistant materials of the spherical annular base member and the outer layer may contain expanded graphite and at least one of 0.05 to 5.00 wt.% of phosphorus pentoxide and 1.0 to 16.0 wt.% of a phosphate.
  • the lubricating composition which is coated on one surface of the composite sheet member may be an aqueous dispersion containing a polytetrafluoroethylene resin.
  • the lubricating composition which is coated on one surface of the composite sheet member may be an aqueous dispersion in which a hexagonal boron nitride powder and a boron oxide powder are dispersedly contained in an alumina sol in which hydrated alumina particles are dispersedly contained in water containing an acid as a dispersion medium, and which exhibits a hydrogen ion concentration of 2 to 3, the aqueous dispersion containing as a solid content 70 to 85 wt.% of hexagonal boron nitride, 0.1 to 10 wt.% of boron oxide, and 5 to 20 wt.% of hydrated alumina.
  • the lubricating composition which is coated on one surface of the composite sheet member may be an aqueous dispersion in which a hexagonal boron nitride powder and a boron oxide powder are dispersedly contained in an alumina sol in which hydrated alumina are dispersedly contained in water containing an acid as a dispersion medium, and which exhibits a hydrogen ion concentration of 2 to 3, the aqueous dispersion being one in which, in a lubricating composition component composed of 70 to 85 wt.% of hexagonal boron nitride, 0.1 to 10 wt.% of boron oxide, and 5 to 20 wt.% of hydrated alumina, a polytetrafluoroethylene resin is contained by not more than 300 parts by weight or not more than 200 parts by weight, preferably 50 to 200 parts by weight or 50 to 150 parts by weight, with respect to 100 parts by weight of that lubricating composition component as a solid content.
  • the acid which is contained in the water as the dispersion medium may be nitric acid, hydrated alumina may be selected from alumina monohydrate such as boehmite or diaspore, alumina trihydrate such as gibbsite or bayerite, and pseudoboehmite.
  • a spherical annular seal member which is capable of preventing as much as possible the damaging and coarsening of the surface of the mating member in the friction with the mating member, and of preventing a decline in sealability and the generation of abnormal frictional noise, as well as a method of manufacturing the same.
  • the aforementioned acidized graphite powder is subjected to heat (expansion) treatment for 1 to 10 seconds at a temperature of 950 to 1200°C to generate pyrolysis gases, to thereby form expanded graphite particles (expansion factor: 240- to 300-fold) expanded by expanding gaps between graphite layers by the gas pressure.
  • An expanded graphite sheet with a desired thickness is fabricated by roll-forming these expanded graphite particles by feeding them to a double-roller apparatus with its roll nip adjusted to a desired nip, and this expanded graphite sheet is used as a heat resistant sheet member I.
  • a solution in which at least one of aqueous orthophosphoric acid of an 84% concentration as a phosphoric acid and aqueous aluminum primary phosphate of a 50% concentration as a phosphate is diluted by methanol is compounded with the acidized graphite material by spraying, and is agitated uniformly to prepare a wet mixture.
  • This wet mixture is dried for 2 hours in the drying furnace held at a temperature of 120°C.
  • this dried mixture is subjected to heat (expansion) treatment for 1 to 10 seconds at a temperature of 950 to 1200°C to generate pyrolysis gases, to thereby form expanded graphite particles (expansion factor: 240- to 300-fold) expanded by expanding gaps between graphite layers by the gas pressure.
  • heat (expansion) treatment for 1 to 10 seconds at a temperature of 950 to 1200°C to generate pyrolysis gases, to thereby form expanded graphite particles (expansion factor: 240- to 300-fold) expanded by expanding gaps between graphite layers by the gas pressure.
  • orthophosphoric acid among the components undergoes dehydration reaction to generate phosphorus pentoxide, while, as for the aluminum primary phosphate, water in its structural formula is desorbed.
  • An expanded graphite sheet with a desired thickness is fabricated by roll-forming these expanded graphite particles by feeding them to a double-roller apparatus with its roll nip adjusted to a desired nip, and these expanded graphite sheets are respectively used as heat resistant sheet members II and III.
  • the expanded graphite which contains at least one of the phosphoric acid and the phosphate permits use at, for example, 500°C or in a high-temperature range exceeding 500°C since the heat resistance of the expanded graphite itself is improved and the oxidation inhibiting action is imparted thereto.
  • the phosphoric acid it is possible to use, in addition to orthophosphoric acid, metaphosphoric acid, polyphosphoric acid, polymetaphosphoric acid, and the like.
  • the phosphate it is possible to use, in addition to the aluminum primary phosphate, lithium primary phosphate, lithium secondary phosphate, calcium primary phosphate, calcium secondary phosphate, aluminum secondary phosphate, and the like.
  • heat-resistant materials I, II, and III as the heat-resistant materials I, II, and III which are used for a spherical annular base member, heat-resistant materials having a density of 1.0 to 1.5 Mg/m 3 , preferably 1.0 to 1.2 Mg/m 3 , at the time of manufacturing the spherical annular seal member are suitably used.
  • heat-resistant materials I, II, and III which are used for an outer layer
  • heat-resistant materials having a density of 0.3- to 0.6-fold the density of the heat-resistant materials I, II, and III used for the aforementioned spherical annular base member at the time of manufacturing the spherical annular seal member, i.e., 0.3 to 0.9 Mg/m 3 , preferably 0.3 to 0.6 Mg/m 3 , are suitably used.
  • a woven metal wire net or a braided wire net is used which is formed by weaving or knitting by using one or more fine metal wires including, as an iron-based wire, a stainless steel wire made of such as austenitic stainless steels SUS 304, SUS 3105, and SUS 316, a ferritic stainless steel SUS 430, or an iron wire (JIS G 3532) or a galvanized iron wire (JIS G 3547), or, as a copper-based wire, a copper-nickel alloy (cupro-nickel) wire, a copper-nickel-zinc alloy (nickel silver) wire, a brass wire, or a beryllium copper wire.
  • a stainless steel wire made of such as austenitic stainless steels SUS 304, SUS 3105, and SUS 316, a ferritic stainless steel SUS 430, or an iron wire (JIS G 3532) or a galvanized iron wire (JIS G 3547)
  • a copper-based wire a copper-
  • the fine metal wire for forming the metal wire net a fine metal wire whose wire diameter is in the range of 0.15 to 0.32 mm, specifically fine metal wires whose wire diameters are 0.15, 0.175, 0.28, and 0.32 mm, are suitably used.
  • the metal wire net as the reinforcing member for the spherical annular base member a fine metal wire having a wire diameter of the upper limit side of the aforementioned range, e.g., 0.28 to 0.32 mm, is suitably used.
  • a metal wire net with a vertical mesh length of 4 to 6 mm or thereabouts and a horizontal mesh length of 3 to 5 mm or thereabouts in Fig. 5 illustrating a braided metal wire net is suitably used.
  • a metal wire net with a vertical mesh length of 2.5 to 3.5 mm and a horizontal mesh length of 1.5 to 2.5 mm in Fig. 5 illustrating the braided metal wire net is suitably used.
  • a lubricating composition for forming a coating layer is used in the form of (1) an aqueous dispersion in which a lubricating composition composed of a polytetrafluoroethylene resin (hereafter abbreviated as "PTFE") powder is contained as a solid content; (2) an aqueous dispersion in which a hexagonal boron nitride powder and a boron oxide powder are dispersedly contained in an alumina sol in which hydrated alumina particles are dispersed in water containing an acid as a dispersion medium, and which exhibits a hydrogen ion concentration of 2 to 3, the aqueous dispersion containing as a solid content a lubricating composition composed of 70 to 85 wt.% of hexagonal boron nitride, 0.1 to 10 wt.% of boron oxide, and 5 to 20 wt.% of hydrated alumina; or (3) an aqueous dispersion containing as a solid content
  • PTFE
  • the hexagonal boron nitride exhibits excellent lubricity particularly in a high-temperature range and accounts for 70 to 85 wt.% as a principal component.
  • the boron oxide, per se, among the components does not exhibit lubricity, but by being contained in the hexagonal boron nitride constituting the principal component, the boron oxide brings out the lubricity inherent in the hexagonal boron nitride and contributes to the reduction of friction particularly in a high-temperature range.
  • its compounding amount is 0.1 to 10 wt.%, preferably 3 to 5 wt.%.
  • the hydrated alumina per se, among the components does not exhibit lubricity, but by being compounded with the aforementioned hexagonal boron nitride and boron oxide, the hydrated alumina improves the adherence of the lubricating composition onto the heat-resistant material surface and demonstrates an effect in the formation of a firm coating layer, and exhibits the function of bringing out the lubricity of the hexagonal boron nitride by promoting the sliding between layers of plate crystals of the hexagonal boron nitride.
  • the compounding amount of hydrated alumina is preferably 5 to 20 wt.%, more preferably 7 to 15 wt.%.
  • the content of the hydrated alumina is less than 5 wt.%, there is no effect on the improvement of the above-described adherence of the lubricating composition, and if it is contained in excess of 20 wt.%, the aqueous dispersion during manufacturing becomes excessively viscous, which aggravates the adhering operation of roller coating, brush coating or the like.
  • the PTFE itself which is contained in the lubricating composition composed of 70 to 85 wt.% of hexagonal boron nitride, 0.1 to 10 wt.% of boron oxide, and 5 to 20 wt.% of hydrated alumina, possesses low frictional properties, and by being contained in the lubricating composition, the PTFE improves the low frictional properties of that lubricating composition, ameliorates the low frictional properties of the coating layer (sliding layer) constituted of that lubricating composition, does not cause a stick-slip phenomenon in the friction with the mating member, and is thereby capable of avoiding as much as possible the generation of abnormal frictional noise attributable to the stick-slip phenomenon, and exhibits the action of enhancing the ductility of the lubricating composition forming. As a result, it is possible to form a film coating layer.
  • the acid which is contained in water serving as a dispersion medium acts as a deflocculant for stabilizing the alumina sol.
  • the acid it is possible to cite as preferable examples inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and amidosulfuric acid, but nitric acid is particularly preferable.
  • the alumina sol one which exhibits a hydrogen ion concentration (pH) of 2 to 3 is recommended. If the hydrogen ion concentration is less than 2, the alumina sol itself becomes unstable, and if the hydrogen ion concentration exceeds 3, the viscosity of the alumina sol becomes high, and the alumina sol is like to coagulate and becomes unstable.
  • the hydrated alumina in the alumina sol is a compound which is expressed by a compositional formula Al 2 O 3 ⁇ nH 2 O (in the compositional formula, 0 ⁇ n ⁇ 3).
  • n is a number which is normally in excess of 0 and less than 3, preferably 0.5 to 2, more preferably 0.7 to 1.5 or thereabouts.
  • alumina monohydrate such as boehmite (Al 2 O 3 ⁇ H 2 O) and diaspore (Al 2 O 3 ⁇ H 2 O)
  • alumina trihydrate such as gibbsite (Al 2 O 3 ⁇ 3H 2 O) and bayerite (Al 2 O 3 ⁇ 3H 2 O), pseudoboehmite, and the like.
  • a belt-shaped metal wire net 4 with a predetermined width D is fabricated by passing into a nip between rollers 2 and 3 a cylindrical braided metal wire net 1 formed by knitting fine metal wires with a wire diameter of 0.15 to 0.32 mm, preferably 0.28 to 0.32 mm, into a cylindrical shape and having a mesh size of 4 to 6 mm or thereabouts (vertical) and 3 to 5 mm or thereabouts (horizontal) (see Fig. 5 ).
  • the belt-shaped metal wire net 4 is cut into a predetermined length L, thereby preparing a reinforcing member 5 for the spherical annular base member.
  • a heat-resistant material (constituted of one of the heat-resistant materials I, II, and III) 6 for the spherical annular base member is prepared which has a density of 1.0 to 1. 5 Mg/m 3 , preferably 1.0 to 1.2 Mg/m 3 , such as to have a width d of 1.10 ⁇ D to 2.10 ⁇ D with respect to the width D of the aforementioned reinforcing member 5 and a length 1 of 1.30 ⁇ L to 2.70 ⁇ L with respect to the length L of the aforementioned reinforcing member 5.
  • a superposed assembly 12 in which the heat-resistant material 6 and the reinforcing member 5 are superposed on top of each other, is obtained as follows: To ensure that the heat-resistant material 6 is wholly exposed at least on a large-diameter-side annular end face 35 which is an annular end face on one axial end side of a partially convex spherical outer surface 34 (see Fig. 2 ) in a spherical annular seal member 39 (see Fig. 1 ) which will be described later, as shown in Fig.
  • the heat-resistant material 6 is made to project in the widthwise direction by 0.1 ⁇ D to 0.8 ⁇ D, at maximum, from one widthwise end 7 of the reinforcing member 5, which becomes the large-diameter-side annular end face 35 of the partially convex spherical outer surface 34. Also, the amount of widthwise projection, ⁇ 1, of the heat-resistant material 6 from the end 7 becomes greater than the amount of its widthwise projection, ⁇ 2, from the other widthwise end 8 of the reinforcing member 5, which becomes a small-diameter side annular end face 36 of the partially convex spherical outer surface 34.
  • the heat-resistant material 6 is made to project in the longitudinal direction by 0.3 ⁇ L to 1.7 ⁇ L, at maximum, from one longitudinal end 9 of the reinforcing member 5. Also, the other longitudinal end 10 of the reinforcing member 5 and a longitudinal end 11 of the heat-resistant material 6 corresponding to that end 10 are made to substantially agree with each other, and the widthwise and lengthwise directions of the reinforcing member 5 and the heat-resistant material 6 are made to agree with each other.
  • the superposed assembly 12 is convoluted spirally with the heat-resistant material 6 placed on the inner side, such that the heat-resistant material 6 is convoluted with one more turn, thereby forming a tubular base member 13 in which the heat-resistant material 6 is exposed on both the inner peripheral side and the outer peripheral side.
  • the heat-resistant material 6 one is prepared in advance which has a length 1 of 1.30 ⁇ L to 2.70 ⁇ L with respect to the length L of the reinforcing member 5 so that the number of winding turns of the heat-resistant material 6 in the tubular base member 13 becomes greater than the number of winding turns of the reinforcing member 5.
  • the tubular base member 13 as shown in Fig.
  • the heat-resistant material 6 on its one widthwise end side projects in the widthwise direction by ⁇ 1 from the one end 7 of the reinforcing member 5, and the heat-resistant material 6 on its other widthwise end side projects in the widthwise direction by ⁇ 2 from the other end 8 of the reinforcing member 5.
  • a heat-resistant material 14 (one of the heat-resistant materials I, II, and III) for the outer layer is separately prepared which has a density of 0.3 to 0.9 Mg/m 3 , preferably 0.3 to 0.6 Mg/m 3 .
  • the heat-resistant material 14 for the outer layer is continuously inserted (see Fig. 9 ) into a reinforcing member 15 for the outer layer constituted of a cylindrical braided metal wire net (the size of the mesh of the braided metal wire net being 2.5 to 3.5 mm (vertical) and 1.5 to 2.5 mm (horizontal)) obtained by continuously knitting fine metal wires with a wire diameter of 0.15 to 0.32 mm, preferably 0.15 to 0.28 mm, by a knitting machine (not shown).
  • a reinforcing member 15 for the outer layer constituted of a cylindrical braided metal wire net (the size of the mesh of the braided metal wire net being 2.5 to 3.5 mm (vertical) and 1.5 to 2.5 mm (horizontal)) obtained by continuously knitting fine metal wires with a wire diameter of 0.15 to 0.32 mm, preferably 0.15 to 0.28 mm, by a knitting machine (not shown).
  • the reinforcing member 15 with that heat-resistant material 14 inserted therein, starting with its insertion-starting end side, is fed into a nip ⁇ 1 between a cylindrical roller 16 having a smooth cylindrical outer peripheral surface and a roller 18 (see Figs. 9 and 10 ) having a cylindrical outer peripheral surface with a plurality of annular recessed grooves 17 along its axial direction, and is thereby pressurized (see Figs. 9 , 11, 12, 13 , and 14 ) in the thicknesswise direction of that heat-resistant material 14.
  • the reinforcing member 15 with the heat-resistant material 14 inserted therein is further fed (see Figs.
  • a flat composite sheet member 21 (see Fig. 16 ) is formed in which the heat-resistant material 14 for the outer layer and the reinforcing member 15 for the outer layer are press bonded to each other such that the heat-resistant material 14 for the outer layer is densely filled in the meshes of the metal wire net of the reinforcing member 15 for the outer layer, and the reinforcing member 15 for the outer layer is embedded in that heat-resistant material 14 for the outer layer, thereby forming the surface of the heat-resistant material 14 for the outer layer and the surface of the reinforcing member 15 for the outer layer flush with each other and allowing the surface of the heat-resistant material 14 and the surface of the reinforcing member 15 to be exposed.
  • This flat composite sheet member 21 is cut into a length of such a measure that it can be wound around the outer peripheral surface of the
  • the nip ⁇ 1 between the cylindrical roller 16 and the roller 18 having the plurality of annular recessed grooves 17 on its outer peripheral surface along the axial direction is preferably set in the range of 0.35 to 0.60 mm, and the nip ⁇ 2 between the pair of rollers 19 and 20 is preferably set in the range of 0.45 to 0.65 mm.
  • a heat-resistant material 14 (one of the heat-resistant materials I, II, and III) for the outer layer is separately prepared which has a density of 0.3 to 0.9 Mg/m 3 , preferably 0.3 to 0.6 Mg/m 3 .
  • the heat-resistant material 14 for the outer layer is continuously inserted (see Fig.
  • a reinforcing member 15 for the outer layer constituted of a cylindrical braided metal wire net (the size of the mesh of the braided metal wire net being 2.5 to 3.5 mm (vertical) and 1.5 to 2.5 mm (horizontal)) obtained by continuously knitting fine metal wires with a wire diameter of 0.15 to 0.32 mm, preferably 0.15 to 0.175 mm, by a knitting machine (not shown).
  • the reinforcing member 15 for the outer layer with that heat-resistant material 14 inserted therein, starting with its insertion-starting end side, is fed into the nip ⁇ 1 between a pair of cylindrical rollers 16a and 18a having smooth cylindrical outer peripheral surfaces, and is thereby pressurized (see Figs.
  • a flat composite sheet member 21 (see Fig. 20 ) is formed in which the heat-resistant material 14 for the outer layer and the reinforcing member 15 for the outer layer are press bonded to each other such that the heat-resistant material 14 for the outer layer is densely filled in the meshes of the metal wire net of the reinforcing member 15 for the outer layer, and the reinforcing member 15 for the outer layer is embedded in that heat-resistant material 14 for the outer layer, thereby forming the surface of the heat-resistant material 14 for the outer layer and the surface of the reinforcing member 15 for the outer layer flush with each other and allowing the surface of the heat-resistant material 14 and the surface of the reinforcing member 15 to be exposed.
  • This flat composite sheet member 21 is cut into a length of such a measure that it can be wound around the outer peripheral surface of the tubular base member 13 by one turn.
  • the nip ⁇ 1 between the aforementioned pair of cylindrical rollers 16a and 18a is preferably set in the range of 0.35 to 0.60 mm. It should be noted that, in the above-described second method as well, a step may be inserted in which the reinforcing member 15 with the heat-resistant material 14 inserted therein is further fed (see Figs. 9 and 15 ) into the nip ⁇ 2 between another pair of cylindrical rollers 19 and 20 having smooth cylindrical outer peripheral surfaces in the above-described first method.
  • a heat-resistant material 14 (one of the heat-resistant materials I, II, and III) for the outer layer is separately prepared which has a width d smaller than the width D of the reinforcing member (belt-shaped metal wire net) for the outer layer and has a density of 0.3 to 0.9 Mg/m 3 , preferably 0.3 to 0.6 Mg/m 3 , in the same way as the heat-resistant material 14 for the outer layer obtained in the above-described fifth process.
  • the reinforcing member 15 for the outer layer made from a cylindrical braided metal wire net formed by knitting fine metal wires with a wire diameter of 0.15 to 0.32 mm, preferably 0.15 to 0.175 mm, is passed into a nip between the pair of cylindrical rollers 2 and 3 to thereby fabricate the belt-shaped metal wire net 4 (see Fig. 3 ).
  • This belt-shaped metal wire net 4 is cut in advance into such a measure that it can be wound around the outer peripheral surface of the tubular base member 13 by one turn.
  • the heat-resistant material 14 for the outer layer is inserted into that belt-shaped metal wire net 4 (see Fig. 21 ).
  • the belt-shaped metal wire net 4 with the heat-resistant material 14 for the outer layer inserted therein is fed into the nip ⁇ 1 between a pair of cylindrical rollers 16b and 18b, and is thereby pressurized in the thicknesswise direction of that heat-resistant material 14 for the outer layer.
  • a flat composite sheet member 21 see Fig.
  • the nip ⁇ 1 between the aforementioned pair of cylindrical rollers 16b and 18b is preferably set in the range of 0.35 to 0.60 mm.
  • the third method may include a step of feeding the belt-shaped metal wire net 4 with the heat-resistant material 14 for the outer layer inserted therein into the nip ⁇ 2 between another pair of cylindrical rollers 19 and 20 having smooth cylindrical outer peripheral surfaces and pressurizing the same by the cylindrical rollers 19 and 20 in the above-described first method.
  • a heat-resistant material 14 (one of the heat-resistant materials I, II, and III) for the outer layer is separately prepared which has the same width as the width D of the reinforcing member (belt-shaped metal wire net) for the outer layer and has a density of 0.3 to 0.9 Mg/m 3 , preferably 0.3 to 0.6 Mg/m 3 , in the same way as the heat-resistant material 14 for the outer layer obtained in the above-described fifth process.
  • a plain woven metal wire net is prepared as a woven metal wire net which is formed by weaving fine metal wires with a wire diameter of 0.15 to 0.32 mm, preferably 0.15 to 0.175 mm.
  • the reinforcing member 15 for the outer layer constituted of this plain woven metal wire net is cut into a predetermined length and width, thereby preparing two reinforcing members 15.
  • the aforementioned heat-resistant material 14 for the outer layer is inserted (placed) between the two reinforcing members 15 for the outer layer, and an assembly thereof is fed into a nip between a pair of cylindrical rollers, and is thereby pressurized in the thicknesswise direction of that heat-resistant material 14.
  • a flat composite sheet member 21 is formed in which the heat-resistant material 14 for the outer layer and the reinforcing member 15 for the outer layer are press bonded to each other such that the heat-resistant material 14 for the outer layer is densely filled in the meshes of the metal wire net of the reinforcing member 15 for the outer layer made from the plain woven metal wire net, and the reinforcing member 15 for the outer layer is embedded in that heat-resistant material 14 for the outer layer, thereby forming the surface of the heat-resistant material 14 for the outer layer and the surface of the reinforcing member 15 for the outer layer flush with each other and allowing the surface of the heat-resistant material 14 for the outer layer and the surface of the reinforcing member 15 for the outer layer to be exposed.
  • This flat composite sheet member 21 is cut into a length of such a measure that it can be wound around the outer peripheral surface of the tubular base member 13 by one turn.
  • the nip between the aforementioned pair of cylindrical rollers is preferably set in the range of 0.35 to 0.60 mm.
  • the above-described fourth method may include a step of feeding the superposed assembly of the heat-resistant material 14 for the outer layer and the two reinforcing members 15 for the outer layer into the nip ⁇ 2 between another pair of cylindrical rollers 19 and 20 having smooth cylindrical outer peripheral surfaces by the cylindrical rollers 19 and 20 in the above-described first method.
  • the ratio of the area of a surface 41 of the reinforcing member 15 for the outer layer, which is exposed together with a surface 52 of the heat-resistant material 14 for the outer layer is preferably 5 to 35 % of the area of the one surface 51 of the composite sheet member 21.
  • the surface roughness of the one surface 51 of the flat composite sheet member 21 having the surface 41 of the reinforcing member 15 for the outer layer, which is exposed together with the surface 52 of the heat-resistant material 14 for the outer layer is preferably 5 to 30 ⁇ m in terms of the arithmetic average roughness Ra.
  • each of the reinforcing members 15 for the outer layer is small after being respectively pressurized by the cylindrical roller 16 and the roller 18 having the plurality of annular recessed grooves 17 on its outer peripheral surface along the axial direction and further by the pair of cylindrical rollers 19 and 20 (the above-described first method), or by the pair of cylindrical rollers 16a and 18a having smooth cylindrical outer peripheral surfaces and, in some cases, further by the pair of cylindrical rollers 19 and 20 (the above-described second method), or by the above-described third and fourth methods.
  • the density of the heat-resistant material 14 for the outer layer is low with a density of 0.3 to 0.9 Mg/m 3 (0.3- to 0.6-fold the density of the heat-resistant material 6 for the spherical annular base member).
  • the heat-resistant material 14 for the outer layer and the reinforcing member 15 for the outer layer are press bonded to each other such that the heat-resistant material 14 for the outer layer is densely filled without gaps in the meshes of the metal wire net of the reinforcing member 15 for the outer layer, and the reinforcing member 15 for the outer layer is embedded in the heat-resistant material 14 of the outer layer.
  • the ratio of the occupying area of the surface 41 of the reinforcing member 15 in an outer layer intermediate surface 42 (see Figs. 1 and 2 ) of an outer layer 38 of the final spherical annular seal member 39 becomes 5 to 35%.
  • the surface roughness of the composite sheet member 21, in which the surface 41 of the reinforcing member 15 is exposed with an area ratio of 5 to 35 % together with the surface 52 of the heat-resistant material 14 of the one surface 51 of the composite sheet member 21, is 5 to 30 ⁇ m in terms of the arithmetic average roughness Ra.
  • One of cylindrical braided metal wire net having a mesh size of 3.5 mm (vertical) and 1.5 mm (horizontal) was fabricated by using an SUS 304 wire with a wire diameter of 0.15 mm and by using an SUS 304 wire with a wire diameter of 0.28 mm, and the other cylindrical braided metal wire net having a mesh size of 3.5 mm (vertical) and 1.5 mm (horizontal) was fabricated by using an SUS 304 wire with a wire diameter of 0.15 mm and by using an SUS 304 wire with a wire diameter of 0.28 mm.
  • a heat-resistant sheet member 14 constituted of expanded graphite and having a density of 0.3 Mg/m 3 and a thickness of 1.5 mm was inserted into a reinforcing member 15 for the outer layer made from each of these cylindrical braided metal wire nets, and composite sheet members 21 were fabricated by setting the nip ⁇ 1 between the cylindrical roller 16 and the roller 18 having the plurality of annular recessed grooves 17 on its outer peripheral surface along the axial direction to 0.40 mm, and by setting the nip ⁇ 2 between the pair of cylindrical rollers 19 and 20 to 0.45 mm.
  • the area ratio of the surface 41 of the reinforcing member 15 which is exposed together with the surface 52 of the heat-resistant material 14 on the surface 51 of the composite sheet member 21 was subjected to image measurement by using the image measurement camera CV-3000 made by Keyence Corporation.
  • the arithmetic average roughness Ra of the one surface 51 of the composite sheet member 21 where the surface 41 of the reinforcing member 15 was exposed measurements were taken of the surface roughness of 60 spots in the widthwise direction and the lengthwise direction of the composite sheet member 21, and the surface roughness is shown by their average values.
  • Fig. 23 is an image measurement photograph of the composite sheet member 21 fabricated by using the cylindrical braided metal wire net fabricated by using the SUS 304 fine metal wire with the wire diameter of 0.15 mm and having the mesh size of 3.5 mm (vertical) and 1.5 mm (horizontal) and the heat-resistant sheet member 14 constituted of expanded graphite and having the density of 0.3 Mg/m 3 and the thickness of 1.5 mm.
  • the ratio of the exposed area of the surface 41 of the reinforcing member 15 for the outer layer was 26.528%.
  • the arithmetic average roughness Ra of the surface 51 of the composite sheet member 21 was 8.34 ⁇ m.
  • Fig. 24 is an image measurement photograph of the composite sheet member 21 fabricated by using the cylindrical braided metal wire net fabricated by using the SUS 304 fine metal wire with the wire diameter of 0.28 mm and having the mesh size of 3.5 mm (vertical) and 1.5 mm (horizontal) and the heat-resistant sheet member 14 constituted of expanded graphite and having the density of 0.3 Mg/m 3 and the thickness of 1.5 mm.
  • the ratio of the exposed area of the surface 41 of the reinforcing member 15 for the outer layer was 23.212%.
  • the arithmetic average roughness Ra of the surface 51 of the composite sheet member 21 was 10.82 ⁇ m.
  • the ratio of the exposed area of the reinforcing member 15 on the one surface 51 of the composite sheet member 21 can be appropriately adjusted in a range of the area ratio of 5 to 35% by appropriately selecting the nip ⁇ 1 between the cylindrical roller 16 and the roller 18 having the plurality of annular recessed grooves 17 on its outer peripheral surface along the axial direction in the range of 0.35 to 0.60 mm, and by setting the nip ⁇ 2 between the pair of cylindrical rollers 19 and 20 in the range of 0.45 to 0.65 mm.
  • the ratio of the exposed area of the reinforcing member 15 on the one surface 51 of the composite sheet member 21 can be appropriately adjusted in a range of the area ratio of 5 to 35% by appropriately selecting the nip ⁇ 1 between the pair of cylindrical rollers 16a and 18a in the range of 0.35 to 0.60 mm.
  • Fig. 25 is an image measurement photograph of a composite sheet member 21a fabricated by the method described in the above-described patent document 3 which is a conventional art. The method of manufacturing this composite sheet member 21a will be described with reference to Figs. 26 to 29 . Namely, by using an austenitic stainless steel wire with a wire diameter of 0.28 mm, a cylindrical braided metal wire net whose mesh size was 4 mm (vertical) and 3 mm (horizontal) was fabricated and was passed between the pair of rollers 2 and 3 to form a belt-shaped metal wire net 4 (see Fig. 3 ). The metal wire net thus formed was used as the reinforcing member 5 for the outer layer.
  • a heat-resistant material containing 0.7 wt.% of phosphorus pentoxide, 4.0 wt.% of aluminum primary phosphate, and expanded graphite, and having a density of 1.12 Mg/m 3 and a thickness of 0.4 mm was used as the heat-resistant material 6 for the outer layer.
  • the area ratio of exposure of a surface 41a of the reinforcing member 5 in a surface 51a of that composite sheet member 21 a was 43.339%, and the arithmetic average roughness Ra of the surface 51a of the composite sheet member 21a was 71.18 ⁇ m.
  • the lubricating composition one of the following is prepared: (1) an aqueous dispersion in which 60 wt.% of a lubricating composition composed of a PTFE powder is contained as a solid content; (2) an aqueous dispersion in which a hexagonal boron nitride powder and a boron oxide powder are dispersedly contained in an alumina sol in which hydrated alumina particles are dispersedly contained in water containing an acid as a dispersion medium, and which exhibits a hydrogen ion concentration (pH) of 2 to 3, the aqueous dispersion containing as a solid content 30 wt.% of a lubricating composition composed of 70 to 85 wt.% of hexagonal boron nitride, 1 to 10 wt.% of boron oxide, and 5 to 20 wt.% of hydrated alumina; and (3) an aqueous dispersion containing as a solid content a lubricating composition composed of 70 to
  • aqueous dispersion (60 wt.% of PTFE and 40 wt.% of water) in which 60 wt.% of the lubricating composition of (1) above, i.e., a lubricating composition constituted of a PTFE powder, was dispersedly contained as a solid content was applied by brush coating to the surface 51 of the composite sheet member 21 fabricated by the above-described first, second, third, or fourth method, and was then allowed to dry, thereby forming an outer layer forming member 23 (see Fig. 30 ) in which a coating layer 22 constituted of that lubricating composition was formed.
  • an aqueous dispersion (35 to 42.5 wt.% of hexagonal boron nitride, 0.05 to 5 wt.% of boron oxide, 2.5 to 10 wt.% of hydrated alumina, and 70 wt.% of water) in which 30 wt.% of the lubricating composition of (2) above, i.e., a lubricating composition composed of 70 to 85 wt.% of hexagonal boron nitride, 0.1 to 10 wt.% of boron oxide, and 5 to 20 wt.% of hydrated alumina, was dispersedly contained as a solid content, was applied by brush coating to the surface 51 of the composite sheet member 21, and was then allowed to dry, thereby forming the outer layer forming member 23 in which the coating layer 22 constituted of that lubricating composition was formed.
  • a lubricating composition composed of 17.5 to 56.7 wt.% of hexagonal boron nitride, 0.025 to 6.7 wt.% of boron oxide, 1.25 to 13.3 wt.% of hydrated alumina, and 33.3 to 75 wt.%
  • alumina monohydrate such as boehmite (Al 2 O 3 ⁇ H 2 O) and diaspore (Al 2 O 3 ⁇ H 2 O)
  • alumina trihydrate such as gibbsite (Al 2 O 3 ⁇ 3H 2 O) and bayerite (Al 2 O 3 ⁇ 3H 2 O), pseudoboehmite, and the like.
  • the outer layer forming member 23 thus obtained is wound around the outer peripheral surface of the tubular base member 13 with the coating layer 22 placed on the outer side, thereby fabricating a cylindrical preform 24 (see Fig. 31 )
  • a die 31 such as the one shown in Fig. 32 is prepared which has on its inner surface a cylindrical inner wall surface 25, a partially convex spherical surface 26 continuing from the cylindrical inner wall surface 25, and a through hole 27 continuing from the partially convex spherical surface 26, and in which a hollow cylindrical portion 29 and a spherical annular hollow portion 30 continuing from that hollow cylindrical portion 29 are formed inside it as a stepped core 28 is inserted in the through hole 27. Then, the cylindrical preform 24 is fitted over the stepped core 28 of the die 31.
  • the cylindrical preform 24 disposed in the hollow cylindrical portion 29 and the spherical annular hollow portion 30 of the die 31 is subjected to compression forming under a pressure of 98 to 392 N/mm 2 (1 to 4 tons/cm 2 ) in the direction of the core axis.
  • a spherical annular seal member 39 is fabricated which includes a spherical annular base member 37 having a through hole 32 in its central portion and defined by a cylindrical inner surface 33, a partially convex spherical surface 34, and the large- and small-diameter-side annular end faces 35 and 36 of the partially convex spherical surface 34, as well as an outer layer 38 formed integrally on the partially convex spherical surface 34 of the spherical annular base member 37.
  • the spherical annular base member 37 is constructed so as to be provided with structural integrity as the heat-resistant material 6 for the spherical annular base member and the reinforcing member 5 for the spherical annular base member are compressed and intertwined with each other.
  • An obverse surface 44 of the outer layer 38 is constituted of a smooth surface 45 of a sliding layer 40 of the lubricating composition adherently formed integrally on the outer layer intermediate surface 42 consisting of a surface 43 of the heat-resistant material 14 for the outer layer and the surface 41 of the reinforcing member 15 for the outer layer which is flush with the surface 43 of the heat-resistant material 14.
  • the tubular base member is formed by spirally convoluting the superposed assembly 12 with the reinforcing member 5 made from the belt-shaped metal wire net 4 placed on the inner side instead of spirally convoluting it with the heat-resistant material 6 placed on the inner side, it is possible to fabricate the spherical annular seal member 39 in which the reinforcing member 5 made from the metal wire net of the spherical annular base member 37 is exposed on the cylindrical inner surface 33.
  • the fabricated spherical annular seal member 39 is comprised of the spherical annular base member 37 defined by the cylindrical inner surface 33, the partially convex spherical surface 34, and the large- and small-diameter-side annular end faces 35 and 36 of the partially convex spherical surface 34, as well as the outer layer 38 formed integrally on the partially convex spherical surface 34 of the spherical annular base member 37.
  • the spherical annular base member 37 includes the reinforcing member 5 made from a metal wire net and the heat-resistant material 6 containing expanded graphite, filling meshes of the metal wire net of the reinforcing member 5, and compressed in such a manner as to be formed integrally with the reinforcing member 5 in mixed form.
  • the outer layer 38 includes a base layer 46 and the sliding layer 40 of the lubricating composition adherently formed integrally on the base layer 46 at the outer layer intermediate surface 42.
  • the base layer 46 includes the reinforcing member 15 made from a metal wire net and compressed and the heat-resistant material 14 constituted of expanded graphite, filling the meshes of the metal wire net of the reinforcing member 15, and compressed so as to be closely press bonded to the reinforcing member 15 and to have the surface 43 flush with the surface 41 of that reinforcing member 15 and forming the outer layer intermediate surface 42 together with that surface 41, the base layer 46 being formed integrally with the partially convex spherical surface 34.
  • the surface roughness of the outer layer intermediate surface 42 is formed with 5 to 30 ⁇ m in the arithmetic average roughness Ra, and the obverse surface 44 of the outer layer 38 exposed to the outside is constituted of the smooth surface 45 of the sliding layer 40.
  • the spherical annular seal member 39 is used by being incorporated in the exhaust pipe spherical joint shown in Fig. 33 . That is, in the exhaust pipe spherical joint shown in Fig. 33 , a flange 102 is provided uprightly on an outer peripheral surface of an upstream-side exhaust pipe 100, which is connected to an engine side, by leaving a pipe end 101.
  • the spherical annular seal member 39 is fitted over the pipe end 101 at the cylindrical inner surface 33 defining the through hole 32, and is seated with its large-diameter-side annular end face 35 abutting against the flange 102.
  • a flared portion 203 which integrally has a concave spherical surface portion 201 and a flange portion 202 connected to the concave spherical surface portion 201, is secured to a downstream-side exhaust pipe 200 which is disposed in face-to-face relation to the upstream-side exhaust pipe 100 and is connected to a muffler side.
  • An inner surface 204 of the concave spherical surface portion 201 is in slidable contact with the smooth surface 45 of the sliding layer 40 in the outer layer 38 of the spherical annular seal member 39.
  • the downstream-side exhaust pipe 200 is constantly urged resiliently toward the upstream-side exhaust pipe 100 by means of a pair of bolts 300 each having one end fixed to the flange 102 and another end arranged by being inserted in the flange portion 202 of the flared portion 203, and by means of a pair of coil springs 400 each arranged between an enlarged head of the bolt 300 and the flange portion 202.
  • the exhaust pipe spherical joint is arranged such that relative angular displacements occurring in the upstream- and downstream-side exhaust pipes 100 and 200 are allowed by sliding contact between the smooth surface 45 of the outer layer 38 of the spherical annular seal member 39 and the inner surface 204 of the concave spherical surface portion 201 of the flared portion 203 formed at the end of the downstream-side exhaust pipe 200.
  • a cylindrical braided metal wire net whose mesh size was 4 mm (vertical) and 5 mm (horizontal) was fabricated and was passed between a pair of rollers to form a belt-shaped metal wire net.
  • the metal wire net thus formed was used as the reinforcing member for the spherical annular base member.
  • an expanded graphite sheet having a density of 1.12 Mg/m 3 and a thickness of 0.4 mm was used.
  • the reinforcing member for the spherical annular base member was superposed on the inner side of the heat-resistant material, and the superposed assembly thereof was spirally convoluted, thereby preparing the tubular base member in which the heat-resistant material was located on the outermost periphery.
  • widthwise opposite end portions of the heat-resistant material respectively projected (jutted out) from the reinforcing member for the spherical annular base member in the widthwise direction.
  • an expanded graphite sheet having a density of 0.3 Mg/m 3 and a thickness of 1.35 mm was used.
  • As the reinforcing member for the outer layer by using an austenitic stainless steel wire (SUS 304) with a wire diameter of 0.28 mm, which was similar to that of the aforementioned reinforcing member for the spherical annular base member, a cylindrical braided metal wire net whose mesh size was 3.5 mm (vertical) and 2.5 mm (horizontal) was continuously knitted, and the heat-resistant material for the outer layer was continuously inserted into the inner side of that cylindrical braided metal wire net.
  • SUS 304 austenitic stainless steel wire
  • the reinforcing member with the heat-resistant material inserted therein starting with its insertion-starting end side of that heat-resistant material, was fed into a nip (the nip ⁇ 1 was set to 0.50 mm) between a cylindrical roller and a roller having a plurality of annular recessed grooves on its outer peripheral surface along the axial direction, and was thereby pressurized in the thicknesswise direction of that heat-resistant material.
  • the reinforcing member with the heat-resistant material inserted therein was further fed into a nip (the nip ⁇ 2 was set to 0.45 mm) between another pair of cylindrical rollers and was thereby pressurized.
  • a flat composite sheet member was formed in which the heat-resistant material for the outer layer and the reinforcing member were press bonded to each other such that the heat-resistant material for the outer layer was densely filled in the meshes of the metal wire net of the reinforcing member, and the reinforcing member was embedded in that heat-resistant material for the outer layer, thereby forming the surface of the heat-resistant material for the outer layer and the surface of the reinforcing member flush with each other and allowing the surface of that reinforcing member and the surface of the heat-resistant material for the outer layer to be exposed in a scattered manner.
  • the area ratio of exposure of the surface of the reinforcing member together with the surface of the heat-resistant material on the one surface of the composite sheet member was 26.4%, and the arithmetic average roughness Ra of that surface was 19.3 ⁇ m
  • an alumina sol was prepared in which boehmite (alumina monohydrate: Al 2 O 3 ⁇ H 2 O) as hydrated alumina was dispersedly contained in water serving as a dispersion medium containing nitric acid acting as a deflocculant, and which exhibited a hydrogen ion concentration (pH) of 2.
  • boehmite alumina monohydrate: Al 2 O 3 ⁇ H 2 O
  • water serving as a dispersion medium containing nitric acid acting as a deflocculant, and which exhibited a hydrogen ion concentration (pH) of 2.
  • An aqueous dispersion A (24.9 wt.% of hexagonal boron nitride, 1.2 wt.% of boron oxide, 3.9 wt.% of boehmite, and 70 wt.% of water and nitric acid) was then prepared which was an aqueous dispersion with a hexagonal boron nitride powder and a boron oxide powder dispersedly contained in this alumina sol, and in which 30 wt.% of a lubricating composition containing 83 wt.% of hexagonal boron nitride, 4 wt.% of boron oxide, and 13 wt.% of boehmite was dispersedly contained as a solid content.
  • aqueous dispersion A was applied by brush coating to that surface of the aforementioned composite sheet member which was pressurized by the aforementioned roller having the annular recessed grooves and was allowed to dry, to thereby fabricate an outer layer forming member in which a coating layer (83 wt.% of hexagonal boron nitride, 4 wt.% of boron oxide, and 13 wt.% of boehmite) of the solid lubricant constituted of the lubricating composition was formed on the surface of that composite sheet member.
  • a coating layer 83 wt.% of hexagonal boron nitride, 4 wt.% of boron oxide, and 13 wt.% of boehmite
  • the above-described outer layer forming member was wound around the outer peripheral surface of the aforementioned tubular base member with the coating layer placed on the outer side, thereby fabricating the cylindrical preform.
  • This cylindrical preform was fitted over the stepped core of the die shown in Fig. 32 , and was placed in the hollow portion of the die.
  • a spherical annular seal member which was comprised of the spherical annular base member having the through hole in its central portion and defined by the cylindrical inner surface, the partially convex spherical surface, and the large- and small-diameter-side annular end faces of the partially convex spherical surface, as well as the outer layer formed integrally on the partially convex spherical surface of the spherical annular base member.
  • the spherical annular base member was constructed so as to be provided with structural integrity as the heat-resistant material for the spherical annular base member and the reinforcing member for the spherical annular base member made from the metal wire net were compressed and intertwined with each other.
  • the spherical annular base member thus had the reinforcing member for the spherical annular base member made from the compressed metal wire net as well as the heat-resistant material for the spherical annular base member which was constituted of expanded graphite and which filled the meshes of this reinforcing member and was compressed in such a manner as to be formed integrally with this reinforcing member in mixed form.
  • the obverse surface of the outer layer was formed into a smooth surface of the sliding layer constituted of the coating layer of the lubricating composition containing 83 wt.% of hexagonal boron nitride, 4 wt.% of boron oxide, and 13 wt.% of boehmite and adherently formed integrally on the base layer at the outer layer intermediate surface consisting of the surface of the heat-resistant material for the outer layer and the surface of the reinforcing member for the outer layer which was flush with the surface of that heat-resistant material.
  • the tubular base member was fabricated in the same way as in Example 1.
  • widthwise opposite end portions of the heat-resistant material respectively projected (jutted out) from the reinforcing member in the widthwise direction.
  • the heat-resistant material for the outer layer an expanded graphite sheet similar to that of the above-described Example 1 was used.
  • As the reinforcing member for the outer layer by using an austenitic stainless steel wire (SUS 304) with a wire diameter of 0.175 mm, a cylindrical braided metal wire net whose mesh size was 3.5 mm (vertical) and 2.5 mm (horizontal) was continuously knitted, and the heat-resistant material for the outer layer was continuously inserted into the inner side of that cylindrical braided metal wire net.
  • SUS 304 austenitic stainless steel wire
  • the reinforcing member with the heat-resistant material inserted therein starting with its insertion-starting end side of that heat-resistant material, was fed into a nip (the nip ⁇ 1 was set to 0.50 mm) between the cylindrical roller and the roller having the plurality of annular recessed grooves on its outer peripheral surface along the axial direction, and was thereby pressurized in the thicknesswise direction of that heat-resistant material.
  • the reinforcing member with the heat-resistant material inserted therein was further fed into a nip (the nip ⁇ 2 was set to 0.45 mm) between another pair of cylindrical rollers and was thereby pressurized.
  • a flat composite sheet member was formed in which the heat-resistant material for the outer layer and the reinforcing member were press bonded to each other such that the heat-resistant material for the outer layer was densely filled in the meshes of the metal wire net of the reinforcing member, and the reinforcing member was embedded in that heat-resistant material for the outer layer, thereby forming the surface of the heat-resistant material for the outer layer and the surface of the reinforcing member flush with each other and allowing the surface of that reinforcing member and the surface of the heat-resistant material for the outer layer to be exposed in a scattered manner.
  • the area ratio of exposure of the surface of the reinforcing member together with the surface of the heat-resistant material on the one surface of the composite sheet member was 23.7%, and the arithmetic average roughness Ra of that surface was 12.6 ⁇ m
  • an aqueous dispersion A (24.9 wt.% of hexagonal boron nitride, 1.2 wt.% of boron oxide, 3.9 wt.% of boehmite, and 70 wt.% of water and nitric acid) was used, and this aqueous dispersion A was applied by brush coating to that surface of the aforementioned composite sheet member which was pressurized by the aforementioned roller having the annular recessed grooves and was allowed to dry, to thereby fabricate an outer layer forming member in which a coating layer (83 wt.% of hexagonal boron nitride, 4 wt.% of boron oxide, and 13 wt.% of boehmite) of the solid lubricant constituted of the lubricating composition was formed on the surface of that composite sheet member.
  • a coating layer 83 wt.% of hexagonal boron nitride, 4 wt.% of boron oxide, and 13
  • the above-described outer layer forming member was wound around the outer peripheral surface of the aforementioned tubular base member with the surface of the coating layer placed on the outer side, thereby fabricating the cylindrical preform. Thereafter, through compression forming similar to that of the above-described Example 1, a spherical annular seal member was obtained which was comprised of the spherical annular base member having the through hole in its central portion and defined by the cylindrical inner surface, the partially convex spherical surface, and the large- and small-diameter-side annular end faces of the partially convex spherical surface, as well as the outer layer formed integrally on the partially convex spherical surface of the spherical annular base member.
  • the spherical annular base member was constructed so as to be provided with structural integrity as the heat-resistant material for the spherical annular base member and the reinforcing member for the spherical annular base member made from the metal wire net were compressed and intertwined with each other.
  • the spherical annular base member thus had the reinforcing member for the spherical annular base member made from the compressed metal wire net as well as the heat-resistant material for the spherical annular base member which was constituted of expanded graphite and which filled the meshes of this reinforcing member and was compressed in such a manner as to be formed integrally with this reinforcing member in mixed form.
  • the obverse surface of the outer layer was formed into a smooth surface of the sliding layer constituted of the coating layer of the lubricating composition containing 83 wt.% of hexagonal boron nitride, 4 wt.% of boron oxide, and 13 wt.% of boehmite and adherently formed integrally on the base layer at the outer layer intermediate surface consisting of the surface of the heat-resistant material for the outer layer and the surface of the reinforcing member for the outer layer which was flush with the surface of that heat-resistant material.
  • the tubular base member was fabricated in the same way as in Example 1.
  • widthwise opposite end portions of the heat-resistant material respectively projected (jutted out) from the reinforcing member in the widthwise direction.
  • the heat-resistant material for the outer layer an expanded graphite sheet similar to that of the above-described Example 1 was used.
  • As the reinforcing member for the outer layer by using an austenitic stainless steel wire (SUS 304) with a wire diameter of 0.15 mm, a cylindrical braided metal wire net whose mesh size was 3.5 mm (vertical) and 2.5 mm (horizontal) was continuously knitted, and the heat-resistant material for the outer layer was continuously inserted into the inner side of that cylindrical braided metal wire net.
  • SUS 304 austenitic stainless steel wire
  • the reinforcing member with the heat-resistant material inserted therein starting with its insertion-starting end side of that heat-resistant material, was fed into a nip (the nip ⁇ 1 was set to 0.50 mm) between the cylindrical roller and the roller having the plurality of annular recessed grooves on its outer peripheral surface along the axial direction, and was thereby pressurized in the thicknesswise direction of that heat-resistant material.
  • the reinforcing member with the heat-resistant material inserted therein was further fed into a nip (the nip ⁇ 2 was set to 0.45 mm) between another pair of cylindrical rollers and was thereby pressurized.
  • a flat composite sheet member was formed in which the heat-resistant material for the outer layer and the reinforcing member were press bonded to each other such that the heat-resistant material for the outer layer was densely filled in the meshes of the metal wire net of the reinforcing member, and the reinforcing member was embedded in that heat-resistant material for the outer layer, thereby forming the surface of the heat-resistant material for the outer layer and the surface of the reinforcing member flush with each other and allowing the surface of that reinforcing member and the surface of the heat-resistant material for the outer layer to be exposed in a scattered manner.
  • the area ratio of exposure of the surface of the reinforcing member together with the surface of the heat-resistant material on the one surface of the composite sheet member was 20.4%, and the arithmetic average roughness Ra of that surface was 8.34 ⁇ m.
  • an aqueous dispersion A (24.9 wt.% of hexagonal boron nitride, 1.2 wt.% of boron oxide, 3.9 wt.% of boehmite, and 70 wt.% of water and nitric acid) was used, and this aqueous dispersion A was applied by brush coating to that surface of the aforementioned composite sheet member which was pressurized by the aforementioned roller having the annular recessed grooves and was allowed to dry, to thereby fabricate an outer layer forming member in which a coating layer (83 wt.% of hexagonal boron nitride, 4 wt.% of boron oxide, and 13 wt.% of boehmite) of the solid lubricant constituted of the lubricating composition was formed on the surface of that composite sheet member.
  • a coating layer 83 wt.% of hexagonal boron nitride, 4 wt.% of boron oxide, and 13
  • the above-described outer layer forming member was wound around the outer peripheral surface of the aforementioned tubular base member with the surface of the coating layer placed on the outer side, thereby fabricating the cylindrical preform. Thereafter, through compression forming similar to that of the above-described Example 1, a spherical annular seal member was obtained which was comprised of the spherical annular base member having the through hole in its central portion and defined by the cylindrical inner surface, the partially convex spherical surface, and the large- and small-diameter-side annular end faces of the partially convex spherical surface, as well as the outer layer formed integrally on the partially convex spherical surface of the spherical annular base member.
  • the spherical annular base member was constructed so as to be provided with structural integrity as the heat-resistant material for the spherical annular base member and the reinforcing member for the spherical annular base member made from the metal wire net were compressed and intertwined with each other.
  • the spherical annular base member thus had the reinforcing member for the spherical annular base member made from the compressed metal wire net as well as the heat-resistant material for the spherical annular base member which was constituted of expanded graphite and which filled the meshes of this reinforcing member and was compressed in such a manner as to be formed integrally with this reinforcing member in mixed form.
  • the obverse surface of the outer layer was formed into a smooth surface of the sliding layer constituted of the coating layer of the lubricating composition containing 83 wt.% of hexagonal boron nitride, 4 wt.% of boron oxide, and 13 wt.% of boehmite and adherently formed integrally on the base layer at the outer layer intermediate surface consisting of the surface of the heat-resistant material for the outer layer and the surface of the reinforcing member for the outer layer which was flush with the surface of that heat-resistant material.
  • the tubular base member was fabricated in the same way as in Example 1.
  • widthwise opposite end portions of the heat-resistant material respectively projected (jutted out) from the reinforcing member in the widthwise direction.
  • a composite sheet member was fabricated by using similar constituent materials and a similar method to those of the above-described Example 1.
  • the area ratio of exposure of the surface of the reinforcing member together with the surface of the heat-resistant material on the one surface of the composite sheet member was 26.2%, and the arithmetic average roughness Ra of that surface was 19.1 ⁇ m.
  • an aqueous dispersion B (60 wt.% of PTFE and 40 wt.% of water and a surface active agent) was prepared in which 60 wt.% of a lubricating composition constituted of a PTFE powder was dispersedly contained as a solid content.
  • This aqueous dispersion B was applied by brush coating to that surface of the aforementioned composite sheet member which was pressurized by the aforementioned roller having the annular recessed grooves and was allowed to dry, to thereby fabricate an outer layer forming member in which a coating layer (100 wt.% of PTFE) of the solid lubricant constituted of the lubricating composition was formed on the surface of that composite sheet member.
  • the above-described outer layer forming member was wound around the outer peripheral surface of the aforementioned tubular base member with the surface of the coating layer placed on the outer side, thereby fabricating the cylindrical preform. Thereafter, through compression forming similar to that of the above-described Example 1, a spherical annular seal member was obtained which was comprised of the spherical annular base member having the through hole in its central portion and defined by the cylindrical inner surface, the partially convex spherical surface, and the large- and small-diameter-side annular end faces of the partially convex spherical surface, as well as the outer layer formed integrally on the partially convex spherical surface of the spherical annular base member.
  • the spherical annular base member was constructed so as to be provided with structural integrity as the heat-resistant material for the spherical annular base member and the reinforcing member for the spherical annular base member made from the metal wire net were compressed and intertwined with each other.
  • the spherical annular base member thus had the reinforcing member for the spherical annular base member made from the compressed metal wire net as well as the heat-resistant material for the spherical annular base member which was constituted of expanded graphite and which filled the meshes of this reinforcing member and was compressed in such a manner as to be formed integrally with this reinforcing member in mixed form.
  • the obverse surface of the outer layer was formed into a smooth surface of the sliding layer constituted of the coating layer of the lubricating composition containing 100 wt.% of PTFE and adherently formed integrally on the base layer at the outer layer intermediate surface consisting of the surface of the heat-resistant material for the outer layer and the surface of the reinforcing member for the outer layer which was flush with the surface of that heat-resistant material.
  • the tubular base member was fabricated in the same way as in Example 1.
  • widthwise opposite end portions of the heat-resistant material respectively projected (jutted out) from the reinforcing member in the widthwise direction.
  • an austenitic stainless steel wire with a wire diameter of 0.15 mm which was similar to that of the above-described Example 3
  • a cylindrical braided metal wire net whose mesh size was 3.5 mm (vertical) and 2.5 mm (horizontal) was continuously knitted, and the heat-resistant material for the outer layer was continuously inserted into the inner side of that cylindrical braided metal wire net.
  • a flat composite sheet member was formed in which the heat-resistant material for the outer layer and the reinforcing member were press bonded to each other such that the heat-resistant material for the outer layer was densely filled in the meshes of the metal wire net of the reinforcing member, and the reinforcing member was embedded in that heat-resistant material for the outer layer, thereby forming the surface of the heat-resistant material for the outer layer and the surface of the reinforcing member for the outer layer flush with each other and allowing the surface of that reinforcing member and the surface of the heat-resistant material to be exposed.
  • the area ratio of exposure of the surface of the reinforcing member together with the surface of the heat-resistant material on the one surface of the composite sheet member was 20.2%, and the arithmetic average roughness Ra of that surface was 8.28 ⁇ m.
  • an aqueous dispersion B (60 wt.% of PTFE and 40 wt.% of water and a surface active agent) similar to that of the above-described Example 4 was used.
  • This aqueous dispersion B was applied by brush coating to one surface of the aforementioned composite sheet member and was allowed to dry, to thereby fabricate an outer layer forming member in which a coating layer (100 wt.% of PTFE) of the solid lubricant constituted of the lubricating composition was formed on the surface of that composite sheet member.
  • the above-described outer layer forming member was wound around the outer peripheral surface of the aforementioned tubular base member with the surface of the coating layer placed on the outer side, thereby fabricating the cylindrical preform. Thereafter, through compression forming similar to that of the above-described Example 1, a spherical annular seal member was obtained which was comprised of the spherical annular base member having the through hole in its central portion and defined by the cylindrical inner surface, the partially convex spherical surface, and the large- and small-diameter-side annular end faces of the partially convex spherical surface, as well as the outer layer formed integrally on the partially convex spherical surface of the spherical annular base member.
  • the spherical annular base member was constructed so as to be provided with structural integrity as the heat-resistant material for the spherical annular base member and the reinforcing member for the spherical annular base member made from the metal wire net were compressed and intertwined with each other.
  • the spherical annular base member thus had the reinforcing member for the spherical annular base member made from the compressed metal wire net as well as the heat-resistant material for the spherical annular base member which was constituted of expanded graphite and which filled the meshes of this reinforcing member and was compressed in such a manner as to be formed integrally with this reinforcing member in mixed form.
  • the obverse surface of the outer layer was formed into a smooth surface of the sliding layer constituted of the coating layer of the lubricating composition containing 100 wt.% of PTFE and adherently formed integrally on the base layer at the outer layer intermediate surface consisting of the surface of the heat-resistant material for the outer layer and the surface of the reinforcing member for the outer layer which was flush with the surface of that heat-resistant material.
  • a reinforcing member for the spherical annular base member similar to that of the above-described Example 1 was used.
  • As the heat-resistant material for the spherical annular base member an expanded graphite sheet containing 4.0 wt.% of aluminum primary phosphate and expanded graphite and having a density of 1.12 Mg/m 3 and a thickness of 0.4 mm was used. After the heat-resistant material was spirally convoluted by a one-circumference portion, the reinforcing member for the outer layer was superposed on the inner side of the heat-resistant material, and the superposed assembly thereof was spirally convoluted, thereby preparing the tubular base member in which the heat-resistant material was located on the outermost periphery. In this tubular base member, widthwise opposite end portions of the heat-resistant material respectively projected (jutted out) from the reinforcing member for the spherical annular base member in the widthwise direction.
  • an expanded graphite sheet containing 4.0 wt.% of aluminum primary phosphate and expanded graphite and having a density of 0.3 Mg/m 3 and a thickness of 1.35 mm was used.
  • As the reinforcing member for the outer layer by using an austenitic stainless steel wire (SUS 304) with a wire diameter of 0.28 mm, which was similar to that of the above-described Example 1, a cylindrical braided metal wire net whose mesh size was 3.5 mm (vertical) and 2.5 mm (horizontal) was continuously knitted, and the heat-resistant material for the outer layer was continuously inserted into the inner side of that cylindrical braided metal wire net.
  • a flat composite sheet member was formed in which the surface of the heat-resistant material for the outer layer and the surface of the reinforcing member for the outer layer was made flush with each other, and the surface of that reinforcing member and the surface of that heat-resistant material were exposed.
  • the area ratio of exposure of the surface of the reinforcing member together with the surface of the heat-resistant material on the one surface of the composite sheet member was 26.6%, and the arithmetic average roughness Ra of that surface was 19.6 ⁇ m.
  • the aqueous dispersion A (24.9 wt.% of hexagonal boron nitride, 1.2 wt.% of boron oxide, 3.9 wt.% of boehmite, and 70 wt.% of water and nitric acid) used in the above-described Example 1 and the aqueous dispersion B (60 wt.% of PTFE and 40 wt.% of water and a surface active agent) used in the above-described Example 4 were prepared.
  • aqueous dispersion C was applied by brush coating to one surface of the aforementioned composite sheet member and was allowed to dry, to thereby form an outer layer forming member in which a coating layer (44.7 wt.% of hexagonal boron nitride, 2.1 wt.% of boron oxide, 7 wt.% of boehmite, and 46.2 wt.% of PTFE) of the solid lubricant constituted of that lubricating composition was formed on the surface of that composite sheet member.
  • a coating layer (44.7 wt.% of hexagonal boron nitride, 2.1 wt.% of boron oxide, 7 wt.% of boehmite, and 46.2 wt.% of PTFE) of the solid lubricant constituted of that lubricating composition was formed on the surface of that composite sheet member.
  • the above-described outer layer forming member was wound around the outer peripheral surface of the aforementioned tubular base member with the surface of the coating layer placed on the outer side, thereby fabricating the cylindrical preform. Thereafter, through compression forming similar to that of the above-described Example 1, a spherical annular seal member was obtained which was comprised of the spherical annular base member having the through hole in its central portion and defined by the cylindrical inner surface, the partially convex spherical surface, and the large- and small-diameter-side annular end faces of the partially convex spherical surface, as well as the outer layer formed integrally on the partially convex spherical surface of the spherical annular base member.
  • the spherical annular base member was constructed so as to be provided with structural integrity as the heat-resistant material for the spherical annular base member and the reinforcing member for the spherical annular base member made from the metal wire net were compressed and intertwined with each other.
  • the spherical annular base member thus had the reinforcing member for the spherical annular base member made from the compressed metal wire net as well as the heat-resistant material for the spherical annular base member which was constituted of expanded graphite and which filled the meshes of this reinforcing member and was compressed in such a manner as to be formed integrally with this reinforcing member in mixed form.
  • the obverse surface of the outer layer was formed into a smooth surface of the sliding layer constituted of the coating layer of the lubricating composition containing 44.7 wt.% of hexagonal boron nitride, 2.1 wt.% of boron oxide, 7 wt.% of boehmite, and 46.2 wt.% of PTFE and adherently formed integrally on the base layer at the outer layer intermediate surface consisting of the surface of the heat-resistant material for the outer layer and the surface of the reinforcing member for the outer layer which was flush with the surface of that heat-resistant material.
  • a reinforcing member for the spherical annular base member similar to that of the above-described Example 1 was used.
  • the reinforcing member for the outer layer was superposed on the inner side of the heat-resistant material, and the superposed assembly thereof was spirally convoluted, thereby preparing the tubular base member in which the heat-resistant material was located on the outermost periphery.
  • widthwise opposite end portions of the heat-resistant material respectively projected (jutted out) from the reinforcing member for the spherical annular base member in the widthwise direction.
  • the heat-resistant material for the outer layer an expanded graphite sheet similar to that of the above-described Example 6 was used.
  • As the reinforcing member for the outer layer by using an austenitic stainless steel wire (SUS 304) with a wire diameter of 0.15 mm, which was similar to that of the above-described Example 3, a cylindrical braided metal wire net whose mesh size was 3.5 mm (vertical) and 2.5 mm (horizontal) was continuously knitted, and the heat-resistant material for the outer layer was continuously inserted into the inner side of that cylindrical braided metal wire net.
  • SUS 304 austenitic stainless steel wire
  • a flat composite sheet member was formed in which the surface of the heat-resistant material for the outer layer and the surface of the reinforcing member for the outer layer was made flush with each other, and the surface of that reinforcing member and the surface of that heat-resistant material were exposed.
  • the area ratio of exposure of the surface of the reinforcing member together with the surface of the heat-resistant material on the one surface of the composite sheet member was 20.4%, and the arithmetic average roughness Ra of that surface was 8.32 ⁇ m.
  • an aqueous dispersion C similar to that of the above-described Example 6 was used as a lubricating composition.
  • This aqueous dispersion C was applied by brush coating to one surface of the aforementioned composite sheet member and was allowed to dry, to thereby form an outer layer forming member in which a coating layer (44.7 wt.% of hexagonal boron nitride, 2.1 wt.% of boron oxide, 7 wt.% of boehmite , and 46.2 wt.% of PTFE) of the solid lubricant constituted of that lubricating composition was formed on the surface of that composite sheet member.
  • a coating layer (44.7 wt.% of hexagonal boron nitride, 2.1 wt.% of boron oxide, 7 wt.% of boehmite , and 46.2 wt.% of PTFE) of the solid lubricant constituted of that lubricating composition was formed on the surface of that
  • the above-described outer layer forming member was wound around the outer peripheral surface of the aforementioned tubular base member with the surface of the coating layer placed on the outer side, thereby fabricating the cylindrical preform. Thereafter, through compression forming similar to that of the above-described Example 1, a spherical annular seal member was obtained which was comprised of the spherical annular base member having the through hole in its central portion and defined by the cylindrical inner surface, the partially convex spherical surface, and the large- and small-diameter-side annular end faces of the partially convex spherical surface, as well as the outer layer formed integrally on the partially convex spherical surface of the spherical annular base member.
  • the spherical annular base member was constructed so as to be provided with structural integrity as the heat-resistant material for the spherical annular base member and the reinforcing member for the spherical annular base member made from the metal wire net were compressed and intertwined with each other.
  • the spherical annular base member thus had the reinforcing member for the spherical annular base member made from the compressed metal wire net as well as the heat-resistant material for the spherical annular base member which was constituted of expanded graphite and which filled the meshes of this reinforcing member and was compressed in such a manner as to be formed integrally with this reinforcing member in mixed form.
  • the obverse surface of the outer layer was formed into a smooth surface of the sliding layer constituted of the coating layer of the lubricating composition containing 44.7 wt.% of hexagonal boron nitride, 2.1 wt.% of boron oxide, 7 wt.% of boehmite, and 46.2 wt.% of PTFE and adherently formed integrally on the base layer at the outer layer intermediate surface consisting of the surface of the heat-resistant material for the outer layer and the surface of the reinforcing member for the outer layer which was flush with the surface of that heat-resistant material.
  • a reinforcing member for the spherical annular base member similar to that of the above-described Example 1 was used.
  • As the heat-resistant material for the spherical annular base member an expanded graphite sheet containing 0.7 wt.% of phosphorus pentoxide, 4.0 wt.% of aluminum primary phosphate, and expanded graphite and having a density of 1.12 Mg/m 3 and a thickness of 0.4 mm was used.
  • the reinforcing member for the outer layer was superposed on the inner side of the heat-resistant material, and the superposed assembly thereof was spirally convoluted, thereby preparing the tubular base member in which the heat-resistant material was located on the outermost periphery.
  • widthwise opposite end portions of the heat-resistant material respectively projected (jutted out) from the reinforcing member for the spherical annular base member in the widthwise direction.
  • an expanded graphite sheet containing 0.7 wt.% of phosphorus pentoxide, 4.0 wt.% of aluminum primary phosphate, and expanded graphite and having a density of 0.3 Mg/m 3 and a thickness of 1.35 mm was used.
  • a reinforcing member for the outer layer a reinforcing member for the outer layer similar to that of the above-described Example 1 was used.
  • a flat composite sheet member was formed in which the surface of the heat-resistant material for the outer layer and the surface of the reinforcing member for the outer layer was made flush with each other, and the surface of that reinforcing member and the surface of that heat-resistant material were exposed.
  • the area ratio of exposure of the surface of the reinforcing member together with the surface of the heat-resistant material on the one surface of the composite sheet member was 26.6%, and the arithmetic average roughness Ra of that surface was 19.6 ⁇ m.
  • the aqueous dispersion A (24.9 wt.% of hexagonal boron nitride, 1.2 wt.% of boron oxide, 3.9 wt.% of boehmite, and 70 wt.% of water and nitric acid) used in the above-described Example 1 and the aqueous dispersion B (60 wt.% of PTFE and 40 wt.% of water and a surface active agent) used in the above-described Example 4 were prepared.
  • aqueous dispersion D was applied by brush coating to that surface of the aforementioned composite sheet member which was pressurized by the aforementioned roller having the annular recessed grooves.
  • This aqueous dispersion D was allowed to dry, to thereby form an outer layer forming member in which a coating layer (40.4 wt.% of hexagonal boron nitride, 2 wt.% of boron oxide, 6.2 wt.% of boehmite, and 51.4 wt.% of PTFE) of the solid lubricant constituted of that lubricating composition was formed on the surface of that composite sheet member.
  • a coating layer (40.4 wt.% of hexagonal boron nitride, 2 wt.% of boron oxide, 6.2 wt.% of boehmite, and 51.4 wt.% of PTFE) of the solid lubricant constituted of that lubricating composition was formed on the surface of that composite sheet member.
  • the above-described outer layer forming member was wound around the outer peripheral surface of the aforementioned tubular base member with the surface of the coating layer placed on the outer side, thereby fabricating the cylindrical preform. Thereafter, through compression forming similar to that of the above-described Example 1, a spherical annular seal member was obtained which was comprised of the spherical annular base member having the through hole in its central portion and defined by the cylindrical inner surface, the partially convex spherical surface, and the large- and small-diameter-side annular end faces of the partially convex spherical surface, as well as the outer layer formed integrally on the partially convex spherical surface of the spherical annular base member.
  • the spherical annular base member was constructed so as to be provided with structural integrity as the heat-resistant material for the spherical annular base member and the reinforcing member for the spherical annular base member made from the metal wire net were compressed and intertwined with each other.
  • the spherical annular base member thus had the reinforcing member for the spherical annular base member made from the compressed metal wire net as well as the heat-resistant material for the spherical annular base member which was constituted of expanded graphite and which filled the meshes of this reinforcing member and was compressed in such a manner as to be formed integrally with this reinforcing member in mixed form.
  • the obverse surface of the outer layer was formed into a smooth surface of the sliding layer constituted of the coating layer of the lubricating composition containing 40.4 wt.% of hexagonal boron nitride, 2 wt.% of boron oxide, 6.2 wt.% of boehmite, and 51.4 wt.% of PTFE and adherently formed integrally on the base layer at the outer layer intermediate surface consisting of the surface of the heat-resistant material for the outer layer and the surface of the reinforcing member for the outer layer which was flush with the surface of that heat-resistant material.
  • a reinforcing member for the spherical annular base member similar to that of the above-described Example 1 was used.
  • As the heat-resistant material for the spherical annular base member an expanded graphite sheet similar to that of the above-described Example 8 was used. After the heat-resistant material was spirally convoluted by a one-circumference portion, the reinforcing member for the outer layer was superposed on the inner side of the heat-resistant material, and the superposed assembly thereof was spirally convoluted, thereby preparing the tubular base member in which the heat-resistant material was located on the outermost periphery. In this tubular base member, widthwise opposite end portions of the heat-resistant material respectively projected (jutted out) from the reinforcing member for the spherical annular base member in the widthwise direction.
  • heat-resistant material for the outer layer an expanded graphite sheet similar to that of the above-described Example 8 was used.
  • reinforcing member for the outer layer a reinforcing member for the outer layer similar to that of the above-described Example 3 was used.
  • a flat composite sheet member was formed in which the surface of the heat-resistant material for the outer layer and the surface of the reinforcing member for the outer layer was made flush with each other, and the surface of that reinforcing member and the surface of that heat-resistant material were exposed.
  • the area ratio of exposure of the surface of the reinforcing member together with the surface of the heat-resistant material on the one surface of the composite sheet member was 20.6%, and the arithmetic average roughness Ra of that surface was 8.6 ⁇ m.
  • an aqueous dispersion D used in the above-described Example 8 was used as a lubricating composition.
  • This aqueous dispersion D was applied by brush coating to one surface of the aforementioned composite sheet member and was allowed to dry, to thereby form an outer layer forming member in which a coating layer (40.4 wt.% of hexagonal boron nitride, 2 wt.% of boron oxide, 6.2 wt.% of boehmite, and 51.4 wt.% of PTFE) of the solid lubricant constituted of that lubricating composition was formed on the surface of that composite sheet member.
  • a coating layer (40.4 wt.% of hexagonal boron nitride, 2 wt.% of boron oxide, 6.2 wt.% of boehmite, and 51.4 wt.% of PTFE) of the solid lubricant constituted of that lubricating composition was formed on the surface of that composite sheet member.
  • the above-described outer layer forming member was wound around the outer peripheral surface of the aforementioned tubular base member with the surface of the coating layer placed on the outer side, thereby fabricating the cylindrical preform. Thereafter, through compression forming similar to that of the above-described Example 1, a spherical annular seal member was obtained which was comprised of the spherical annular base member having the through hole in its central portion and defined by the cylindrical inner surface, the partially convex spherical surface, and the large- and small-diameter-side annular end faces of the partially convex spherical surface, as well as the outer layer formed integrally on the partially convex spherical surface of the spherical annular base member.
  • the spherical annular base member was constructed so as to be provided with structural integrity as the heat-resistant material for the spherical annular base member and the reinforcing member for the spherical annular base member made from the metal wire net were compressed and intertwined with each other.
  • the spherical annular base member thus had the reinforcing member for the spherical annular base member made from the compressed metal wire net as well as the heat-resistant material for the spherical annular base member which was constituted of expanded graphite and which filled the meshes of this reinforcing member and was compressed in such a manner as to be formed integrally with this reinforcing member in mixed form.
  • the obverse surface of the outer layer was formed into a smooth surface of the sliding layer constituted of the coating layer of the lubricating composition containing 40.4 wt.% of hexagonal boron nitride, 2 wt.% of boron oxide, 6.2 wt.% of boehmite, and 51.4 wt.% of PTFE and adherently formed integrally on the base layer at the outer layer intermediate surface consisting of the surface of the heat-resistant material for the outer layer and the surface of the reinforcing member for the outer layer which was flush with the surface of that heat-resistant material.
  • a reinforcing member for the spherical annular base member similar to that of the above-described Example 1 was used.
  • As the heat-resistant material for the spherical annular base member an expanded graphite sheet similar to that of the above-described Example 8 was used. After the heat-resistant material was spirally convoluted by a one-circumference portion, the reinforcing member for the outer layer was superposed on the inner side of the heat-resistant material, and the superposed assembly thereof was spirally convoluted, thereby preparing the tubular base member in which the heat-resistant material was located on the outermost periphery. In this tubular base member, widthwise opposite end portions of the heat-resistant material respectively projected (jutted out) from the reinforcing member for the spherical annular base member in the widthwise direction.
  • the heat-resistant material for the outer layer an expanded graphite sheet similar to that of the above-described Example 8 was used.
  • the reinforcing member for the outer layer a reinforcing member for the outer layer similar to that of the above-described Example 1 was used.
  • a flat composite sheet member was formed in which the surface of the heat-resistant material for the outer layer and the surface of the reinforcing member for the outer layer was made flush with each other, and the surface of that reinforcing member and the surface of that heat-resistant material were exposed.
  • the area ratio of exposure of the surface of the reinforcing member together with the surface of the heat-resistant material on the one surface of the composite sheet member was 26.4%, and the arithmetic average roughness Ra of that surface was 19.2 ⁇ m.
  • the aqueous dispersion A (24.9 wt.% of hexagonal boron nitride, 1.2 wt.% of boron oxide, 3.9 wt.% of boehmite, and 70 wt.% of water and nitric acid) used in the above-described Example 1 and the aqueous dispersion B (60 wt.% of PTFE and 40 wt.% of water and a surface active agent) used in the above-described Example 4 were prepared.
  • aqueous dispersion E was applied by brush coating to that surface of the aforementioned composite sheet member which was pressurized by the aforementioned roller having the annular recessed grooves.
  • This aqueous dispersion D was allowed to dry, to thereby form an outer layer forming member in which a coating layer (27.7 wt.% of hexagonal boron nitride, 1.3 wt.% of boron oxide, 4.3 wt.% of boehmite, and 66.7 wt.% of PTFE) of the solid lubricant constituted of that lubricating composition was formed on the surface of that composite sheet member.
  • a coating layer 27.7 wt.% of hexagonal boron nitride, 1.3 wt.% of boron oxide, 4.3 wt.% of boehmite, and 66.7 wt.% of PTFE
  • the above-described outer layer forming member was wound around the outer peripheral surface of the aforementioned tubular base member with the surface of the coating layer placed on the outer side, thereby fabricating the cylindrical preform. Thereafter, through compression forming similar to that of the above-described Example 1, a spherical annular seal member was obtained which was comprised of the spherical annular base member having the through hole in its central portion and defined by the cylindrical inner surface, the partially convex spherical surface, and the large- and small-diameter-side annular end faces of the partially convex spherical surface, as well as the outer layer formed integrally on the partially convex spherical surface of the spherical annular base member.
  • the spherical annular base member was constructed so as to be provided with structural integrity as the heat-resistant material for the spherical annular base member and the reinforcing member for the spherical annular base member made from the metal wire net were compressed and intertwined with each other.
  • the spherical annular base member thus had the reinforcing member for the spherical annular base member made from the compressed metal wire net as well as the heat-resistant material for the spherical annular base member which was constituted of expanded graphite and which filled the meshes of this reinforcing member and was compressed in such a manner as to be formed integrally with this reinforcing member in mixed form.
  • the obverse surface of the outer layer was formed into a smooth surface of the sliding layer constituted of the coating layer of the lubricating composition containing 27.7 wt.% of hexagonal boron nitride, 1.3 wt.% of boron oxide, 4.3 wt.% of boehmite, and 66.7 wt.% of PTFE and adherently formed integrally on the base layer at the outer layer intermediate surface consisting of the surface of the heat-resistant material for the outer layer and the surface of the reinforcing member for the outer layer which was flush with the surface of that heat-resistant material.
  • a reinforcing member for the spherical annular base member similar to that of the above-described Example 1 was used.
  • As the heat-resistant material for the spherical annular base member an expanded graphite sheet similar to that of the above-described Example 8 was used. After the heat-resistant material was spirally convoluted by a one-circumference portion, the reinforcing member for the outer layer was superposed on the inner side of the heat-resistant material, and the superposed assembly thereof was spirally convoluted, thereby preparing the tubular base member in which the heat-resistant material was located on the outermost periphery. In this tubular base member, widthwise opposite end portions of the heat-resistant material respectively projected (jutted out) from the reinforcing member for the spherical annular base member in the widthwise direction.
  • the heat-resistant material for the outer layer an expanded graphite sheet similar to that of the above-described Example 8 was used.
  • the reinforcing member for the outer layer a reinforcing member for the outer layer similar to that of the above-described Example 3 was used. Thereafter, in a method similar to that of the above-described Example 5, a flat composite sheet member was formed in which the surface of the heat-resistant material for the outer layer and the surface of the reinforcing member for the outer layer was made flush with each other, and the surface of that reinforcing member and the surface of that heat-resistant material were exposed.
  • the area ratio of exposure of the surface of the reinforcing member together with the surface of the heat-resistant material on the one surface of the composite sheet member was 20.3%, and the arithmetic average roughness Ra of that surface was 8.3 ⁇ m.
  • an aqueous dispersion E similar to that of the above-described Example 10 was used.
  • This aqueous dispersion E was applied by brush coating to one surface of the aforementioned composite sheet member and was allowed to dry, to thereby form an outer layer forming member in which a coating layer (27.7 wt.% of hexagonal boron nitride, 1.3 wt.% of boron oxide, 4.3 wt.% of boehmite, and 66.7 wt.% of PTFE) of the solid lubricant constituted of that lubricating composition was formed on the surface of that composite sheet member.
  • a coating layer 27.7 wt.% of hexagonal boron nitride, 1.3 wt.% of boron oxide, 4.3 wt.% of boehmite, and 66.7 wt.% of PTFE
  • the above-described outer layer forming member was wound around the outer peripheral surface of the aforementioned tubular base member with the surface of the coating layer placed on the outer side, thereby fabricating the cylindrical preform. Thereafter, through compression forming similar to that of the above-described Example 1, a spherical annular seal member was obtained which was comprised of the spherical annular base member having the through hole in its central portion and defined by the cylindrical inner surface, the partially convex spherical surface, and the large- and small-diameter-side annular end faces of the partially convex spherical surface, as well as the outer layer formed integrally on the partially convex spherical surface of the spherical annular base member.
  • the spherical annular base member was constructed so as to be provided with structural integrity as the heat-resistant material for the spherical annular base member and the reinforcing member for the spherical annular base member made from the metal wire net were compressed and intertwined with each other.
  • the spherical annular base member thus had the reinforcing member for the spherical annular base member made from the compressed metal wire net as well as the heat-resistant material for the spherical annular base member which was constituted of expanded graphite and which filled the meshes of this reinforcing member and was compressed in such a manner as to be formed integrally with this reinforcing member in mixed form.
  • the obverse surface of the outer layer was formed into a smooth surface of the sliding layer constituted of the coating layer of the lubricating composition containing 27.7 wt.% of hexagonal boron nitride, 1.3 wt.% of boron oxide, 4.3 wt.% of boehmite, and 66.7 wt.% of PTFE and adherently formed integrally on the base layer at the outer layer intermediate surface consisting of the surface of the heat-resistant material for the outer layer and the surface of the reinforcing member for the outer layer which was flush with the surface of that heat-resistant material.
  • a reinforcing member for the spherical annular base member similar to that of the above-described Example 1 was used.
  • As the heat-resistant material for the spherical annular base member an expanded graphite sheet similar to that of the above-described Example 8 was used. After the heat-resistant material was spirally convoluted by a one-circumference portion, the reinforcing member for the outer layer was superposed on the inner side of the heat-resistant material, and the superposed assembly thereof was spirally convoluted, thereby preparing the tubular base member in which the heat-resistant material was located on the outermost periphery. In this tubular base member, widthwise opposite end portions of the heat-resistant material respectively projected (jutted out) from the reinforcing member for the spherical annular base member in the widthwise direction.
  • the heat-resistant material for the outer layer an expanded graphite sheet similar to that of the above-described Example 8 was used.
  • the reinforcing member for the outer layer a reinforcing member for the outer layer similar to that of the above-described Example 1 was used.
  • a flat composite sheet member was formed in which the surface of the heat-resistant material for the outer layer and the surface of the reinforcing member for the outer layer was made flush with each other, and the surface of that reinforcing member and the surface of that heat-resistant material were exposed.
  • the area ratio of exposure of the surface of the reinforcing member together with the surface of the heat-resistant material on the one surface of the composite sheet member was 26.5%, and the arithmetic average roughness Ra of that surface was 19.4 ⁇ m.
  • the aqueous dispersion A (24.9 wt.% of hexagonal boron nitride, 1.2 wt.% of boron oxide, 3.9 wt.% of boehmite, and 70 wt.% of water and nitric acid) used in the above-described Example 1 and the aqueous dispersion B (60 wt.% of PTFE and 40 wt.% of water and a surface active agent) used in the above-described Example 4 were prepared.
  • aqueous dispersion F was applied by brush coating to that surface of the aforementioned composite sheet member which was pressurized by the aforementioned roller having the annular recessed grooves.
  • This aqueous dispersion D was allowed to dry, to thereby form an outer layer forming member in which a coating layer (20.8 wt.% of hexagonal boron nitride, 1.0 wt.% of boron oxide, 3.2 wt.% of boehmite, and 75 wt.% of PTFE) of the solid lubricant constituted of that lubricating composition was formed on the surface of that composite sheet member.
  • the above-described outer layer forming member was wound around the outer peripheral surface of the aforementioned tubular base member with the surface of the coating layer placed on the outer side, thereby fabricating the cylindrical preform. Thereafter, through compression forming similar to that of the above-described Example 1, a spherical annular seal member was obtained which was comprised of the spherical annular base member having the through hole in its central portion and defined by the cylindrical inner surface, the partially convex spherical surface, and the large- and small-diameter-side annular end faces of the partially convex spherical surface, as well as the outer layer formed integrally on the partially convex spherical surface of the spherical annular base member.
  • the spherical annular base member was constructed so as to be provided with structural integrity as the heat-resistant material for the spherical annular base member and the reinforcing member for the spherical annular base member made from the metal wire net were compressed and intertwined with each other.
  • the spherical annular base member thus had the reinforcing member for the spherical annular base member made from the compressed metal wire net as well as the heat-resistant material for the spherical annular base member which was constituted of expanded graphite and which filled the meshes of this reinforcing member and was compressed in such a manner as to be formed integrally with this reinforcing member in mixed form.
  • the obverse surface of the outer layer was formed into a smooth surface of the sliding layer constituted of the coating layer of the lubricating composition containing 20.8 wt.% of hexagonal boron nitride, 1.0 wt.% of boron oxide, 3.2 wt.% of boehmite, and 75 wt.% of PTFE and adherently formed integrally on the base layer at the outer layer intermediate surface consisting of the surface of the heat-resistant material for the outer layer and the surface of the reinforcing member for the outer layer which was flush with the surface of that heat-resistant material.
  • a reinforcing member for the spherical annular base member similar to that of the above-described Example 1 was used.
  • As the heat-resistant material for the spherical annular base member an expanded graphite sheet similar to that of the above-described Example 8 was used. After the heat-resistant material was spirally convoluted by a one-circumference portion, the reinforcing member for the outer layer was superposed on the inner side of the heat-resistant material, and the superposed assembly thereof was spirally convoluted, thereby preparing the tubular base member in which the heat-resistant material was located on the outermost periphery. In this tubular base member, widthwise opposite end portions of the heat-resistant material respectively projected (jutted out) from the reinforcing member for the spherical annular base member in the widthwise direction.
  • the heat-resistant material for the outer layer an expanded graphite sheet similar to that of the above-described Example 8 was used.
  • the reinforcing member for the outer layer a reinforcing member for the outer layer similar to that of the above-described Example 3 was used. Thereafter, in a method similar to that of the above-described Example 5, a flat composite sheet member was formed in which the surface of the heat-resistant material for the outer layer and the surface of the reinforcing member for the outer layer was made flush with each other, and the surface of that reinforcing member and the surface of that heat-resistant material were exposed.
  • the area ratio of exposure of the surface of the reinforcing member together with the surface of the heat-resistant material on the one surface of the composite sheet member was 20.3%, and the arithmetic average roughness Ra of that surface was 8.3 ⁇ m.
  • an aqueous dispersion F similar to that of the above-described Example 12 was used.
  • This aqueous dispersion F was applied by brush coating to one surface of the aforementioned composite sheet member and was allowed to dry, to thereby form an outer layer forming member in which a coating layer (20.8 wt.% of hexagonal boron nitride, 1.0 wt.% of boron oxide, 3.2 wt.% of boehmite, and 75 wt.% of PTFE) of the solid lubricant constituted of that lubricating composition was formed on the surface of that composite sheet member.
  • a coating layer (20.8 wt.% of hexagonal boron nitride, 1.0 wt.% of boron oxide, 3.2 wt.% of boehmite, and 75 wt.% of PTFE
  • the above-described outer layer forming member was wound around the outer peripheral surface of the aforementioned tubular base member with the surface of the coating layer placed on the outer side, thereby fabricating the cylindrical preform. Thereafter, through compression forming similar to that of the above-described Example 1, a spherical annular seal member was obtained which was comprised of the spherical annular base member having the through hole in its central portion and defined by the cylindrical inner surface, the partially convex spherical surface, and the large- and small-diameter-side annular end faces of the partially convex spherical surface, as well as the outer layer formed integrally on the partially convex spherical surface of the spherical annular base member.
  • the spherical annular base member was constructed so as to be provided with structural integrity as the heat-resistant material for the spherical annular base member and the reinforcing member for the spherical annular base member made from the metal wire net were compressed and intertwined with each other.
  • the spherical annular base member thus had the reinforcing member for the spherical annular base member made from the compressed metal wire net as well as the heat-resistant material for the spherical annular base member which was constituted of expanded graphite and which filled the meshes of this reinforcing member and was compressed in such a manner as to be formed integrally with this reinforcing member in mixed form.
  • the obverse surface of the outer layer was formed into a smooth surface of the sliding layer constituted of the coating layer of the lubricating composition containing 20.8 wt.% of hexagonal boron nitride, 1.0 wt.% of boron oxide, 3.2 wt.% of boehmite, and 75 wt.% of PTFE and adherently formed integrally on the base layer at the outer layer intermediate surface consisting of the surface of the heat-resistant material for the outer layer and the surface of the reinforcing member for the outer layer which was flush with the surface of that heat-resistant material.
  • an austenitic stainless steel wire SUS 304 having a wire diameter of 0.28 mm as a fine metal wire
  • a cylindrical braided metal wire net whose mesh size was 4 mm (vertical) and 5 mm (horizontal) was fabricated and was passed between a pair of rollers to form a belt-shaped metal wire net.
  • the metal wire net thus formed was used as the reinforcing member for the spherical annular base member.
  • the heat-resistant sheet member for the spherical annular base member a heat-resistant sheet member containing 0.7 wt.% of phosphorus pentoxide, 4.0 wt.% of aluminum primary phosphate, and expanded graphite and having a density of 1.12 Mg/m 3 and a thickness of 0.4 mm was used. After the heat-resistant sheet member was spirally convoluted by a one-circumference portion, the reinforcing member was superposed on the inner side of the heat-resistant sheet member, and the superposed assembly thereof was spirally convoluted, thereby preparing the tubular base member in which the heat-resistant sheet member was located on the outermost periphery. In this tubular base member, widthwise opposite end portions of the heat-resistant sheet member respectively projected from the reinforcing member in the widthwise direction.
  • heat-resistant sheet member for the outer layer a heat-resistant sheet member containing 0.7 wt.% of phosphorus pentoxide, 4.0 wt.% of aluminum primary phosphate, and expanded graphite and having a density of 0.3 Mg/m 3 and a thickness of 1.35 mm was used.
  • the reinforcing member for the outer layer by using an austenitic stainless steel wire with a wire diameter of 0.28 mm in the same way as the aforementioned reinforcing member for the spherical annular base member, a cylindrical braided metal wire net whose mesh size was 3.5 mm (vertical) and 2.5 mm (horizontal) was continuously knitted, and the heat-resistant sheet member for the outer layer was continuously inserted into the inner side of that cylindrical braided metal wire net.
  • the reinforcing member with the heat-resistant sheet member inserted therein starting with its insertion-starting end side of that heat-resistant sheet member, was fed into a nip (the nip ⁇ 1 was set to 0.50 mm) between a cylindrical roller and a roller having a plurality of annular recessed grooves on its outer peripheral surface along the axial direction, and was thereby pressurized.
  • the reinforcing member with the heat-resistant sheet member inserted therein was further fed into a nip (the nip ⁇ 2 was set to 0.45 mm) between another pair of cylindrical rollers and was thereby pressurized.
  • a flat composite sheet member was formed in which the heat-resistant sheet member for the outer layer and the reinforcing member were press bonded to each other such that the heat-resistant sheet member for the outer layer was densely filled in the meshes of the metal wire net of the reinforcing member, and the reinforcing member was embedded in that heat-resistant sheet member for the outer layer, thereby forming the surface of the heat-resistant sheet member for the outer layer and the surface of the reinforcing member flush with each other and allowing the surface of that reinforcing member and the surface of the heat-resistant sheet member for the outer layer to be exposed.
  • the area ratio of exposure of the surface of the reinforcing member together with the surface of the heat-resistant material on the one surface of the composite sheet member was 26.4%, and the arithmetic average roughness Ra of that surface was 19.3 ⁇ m.
  • an aqueous dispersion (43 wt.% of hexagonal boron nitride, 2 wt.% of boron oxide, 5 wt.% of boehmite, and 50 wt.% of water) was prepared which was an aqueous dispersion formed with a hexagonal boron nitride powder and a boron oxide powder dispersedly contained in an alumina sol in which boehmite (alumina monohydrate: Al 2 O 3 ⁇ H 2 O) particles as hydrated alumina were dispersedly contained in water (dispersion medium) containing nitric acid, and which exhibited a hydrogen ion concentration (pH) of 2.
  • boehmite alumina monohydrate: Al 2 O 3 ⁇ H 2 O
  • a coating operation was repeated three times in which this aqueous dispersion was applied by brush coating to that surface of the aforementioned composite sheet member which was pressurized by the aforementioned roller having the annular recessed grooves and was allowed to dry at a temperature of 100°C.
  • An outer layer forming member was thereby fabricated in which a coating layer (86 wt.% of hexagonal boron nitride, 4 wt.% of boron oxide, and 10 wt.% of boehmite) of the lubricating composition was formed on the one surface of that composite sheet member.
  • the above-described outer layer forming member was wound around the outer peripheral surface of the aforementioned tubular base member with the surface of the coating layer placed on the outer side, thereby fabricating the cylindrical preform.
  • This cylindrical preform was fitted over the stepped core of the die shown in Fig. 26 , and was placed in the hollow portion of the die.
  • a spherical annular seal member which was comprised of the spherical annular base member having the through hole in its central portion and defined by the cylindrical inner surface, the partially convex spherical surface, and the large- and small-diameter-side annular end faces of the partially convex spherical surface, as well as the outer layer formed integrally on the partially convex spherical surface of the spherical annular base member.
  • the spherical annular base member was constructed so as to be provided with structural integrity as the heat-resistant material for the spherical annular base member and the reinforcing member for the spherical annular base member made from the metal wire net were compressed and intertwined with each other.
  • the spherical annular base member thus had the reinforcing member for the spherical annular base member made from the compressed metal wire net as well as the heat-resistant material for the spherical annular base member which was constituted of expanded graphite and which filled the meshes of this reinforcing member and was compressed in such a manner as to be formed integrally with this reinforcing member in mixed form.
  • the obverse surface of the outer layer was formed into a smooth surface of the sliding layer constituted of the coating layer of the lubricating composition and adherently formed integrally on the base layer at the outer layer intermediate surface consisting of the surface of the heat-resistant material for the outer layer and the surface of the reinforcing member for the outer layer which was flush with the surface of that heat-resistant material.
  • the tubular base member was fabricated in the same way as in the above-described Example 14. In this tubular base member, widthwise opposite end portions of the heat-resistant sheet member respectively projected from the reinforcing member in the widthwise direction.
  • heat-resistant sheet member for the outer layer a heat-resistant sheet member similar to that of the above-described Example 14 was used.
  • the reinforcing member for the outer layer by using an austenitic stainless steel wire (SUS 304) with a wire diameter of 0.175 mm, a cylindrical braided metal wire net whose mesh size was 3.5 mm (vertical) and 2.5 mm (horizontal) was continuously knitted, and the heat-resistant sheet member for the outer layer was continuously inserted into the inner side of that cylindrical braided metal wire net.
  • SUS 304 austenitic stainless steel wire
  • the reinforcing member with the heat-resistant sheet member inserted therein starting with its insertion-starting end side of that heat-resistant sheet member, was fed into a nip (the nip ⁇ 1 was set to 0.50 mm) between the cylindrical roller and the roller having the plurality of annular recessed grooves on its outer peripheral surface along the axial direction, and was thereby pressurized.
  • the reinforcing member with the heat-resistant sheet member inserted therein was further fed into a nip (the nip ⁇ 2 was set to 0.45 mm) between another pair of cylindrical rollers and was thereby pressurized.
  • a flat composite sheet member was formed in which the heat-resistant sheet member for the outer layer and the reinforcing member were press bonded to each other such that the heat-resistant sheet member for the outer layer was densely filled in the meshes of the metal wire net of the reinforcing member, and the reinforcing member was embedded in that heat-resistant sheet member for the outer layer, thereby forming the surface of the heat-resistant sheet member for the outer layer and the surface of the reinforcing member flush with each other and allowing the surface of that reinforcing member and the surface of the heat-resistant sheet member for the outer layer to be exposed.
  • the area ratio of exposure of the surface of the reinforcing member together with the surface of the heat-resistant material on the one surface of the composite sheet member was 23.7%, and the arithmetic average roughness Ra of that surface was 12.6 ⁇ m.
  • an aqueous dispersion (43 wt.% of hexagonal boron nitride, 2 wt.% of boron oxide, 5 wt.% of boehmite, and 50 wt.% of water), which was similar to that of the above-described Example 14, was used.
  • a coating operation was repeated three times in which this aqueous dispersion was applied by brush coating to that surface of the aforementioned composite sheet member which was pressurized by the aforementioned roller having the annular recessed grooves and was allowed to dry at a temperature of 100°C.
  • An outer layer forming member was thereby fabricated in which a coating layer (86 wt.% of hexagonal boron nitride, 4 wt.% of boron oxide, and 10 wt.% of boehmite) of the lubricating composition was formed on the one surface of that composite sheet member.
  • a spherical annular seal member which was comprised of the spherical annular base member having the through hole in its central portion and defined by the cylindrical inner surface, the partially convex spherical surface, and the large- and small-diameter-side annular end faces of the partially convex spherical surface, as well as the outer layer formed integrally on the partially convex spherical surface of the spherical annular base member.
  • the tubular base member was fabricated in the same way as in the above-described Example 14. In this tubular base member, widthwise opposite end portions of the heat-resistant sheet member respectively projected from the reinforcing member in the widthwise direction.
  • heat-resistant sheet member for the outer layer a heat-resistant sheet member similar to that of the above-described Example 14 was used.
  • the reinforcing member for the outer layer by using an austenitic stainless steel wire (SUS 304) with a wire diameter of 0.15 mm, a cylindrical braided metal wire net whose mesh size was 3.5 mm (vertical) and 2.5 mm (horizontal) was continuously knitted, and the heat-resistant sheet member for the outer layer was continuously inserted into the inner side of that cylindrical braided metal wire net.
  • SUS 304 austenitic stainless steel wire
  • the reinforcing member with the heat-resistant sheet member inserted therein starting with its insertion-starting end side of that heat-resistant sheet member, was fed into a nip (the nip ⁇ 1 was set to 0.50 mm) between the cylindrical roller and the roller having the plurality of annular recessed grooves on its outer peripheral surface along the axial direction, and was thereby pressurized.
  • the reinforcing member with the heat-resistant sheet member inserted therein was further fed into a nip (the nip ⁇ 2 was set to 0.45 mm) between another pair of cylindrical rollers and was thereby pressurized.
  • a flat composite sheet member was formed in which the heat-resistant sheet member for the outer layer and the reinforcing member were press bonded to each other such that the heat-resistant sheet member for the outer layer was densely filled in the meshes of the metal wire net of the reinforcing member, and the reinforcing member was embedded in that heat-resistant sheet member for the outer layer, thereby forming the surface of the heat-resistant sheet member for the outer layer and the surface of the reinforcing member flush with each other and allowing the surface of that reinforcing member and the surface of the heat-resistant sheet member for the outer layer to be exposed.
  • the area ratio of exposure of the surface of the reinforcing member together with the surface of the heat-resistant material on the one surface of the composite sheet member was 20.4%, and the arithmetic average roughness Ra of that surface was 8.34 ⁇ m.
  • an aqueous dispersion (43 wt.% of hexagonal boron nitride, 2 wt.% of boron oxide, 5 wt.% of boehmite, and 50 wt.% of water), which was similar to that of the above-described Example 14, was used.
  • a coating operation was repeated three times in which this aqueous dispersion was applied by brush coating to that surface of the aforementioned composite sheet member which was pressurized by the aforementioned roller having the annular recessed grooves and was allowed to dry at a temperature of 100°C.
  • An outer layer forming member was thereby fabricated in which a coating layer (86 wt.% of hexagonal boron nitride, 4 wt.% of boron oxide, and 10 wt.% of boehmite) of the lubricating composition was formed on the one surface of that composite sheet member.
  • a spherical annular seal member which was comprised of the spherical annular base member having the through hole in its central portion and defined by the cylindrical inner surface, the partially convex spherical surface, and the large- and small-diameter-side annular end faces of the partially convex spherical surface, as well as the outer layer formed integrally on the partially convex spherical surface of the spherical annular base member.
  • the tubular base member was fabricated in the same way as in the above-described Example 14. In this tubular base member, widthwise opposite end portions of the heat-resistant sheet member respectively projected from the reinforcing member in the widthwise direction.
  • a flat composite sheet member was fabricated by using similar materials and a similar method to those of the above-described Example 14. In this composite sheet member, the area ratio of exposure of the surface of the reinforcing member together with the surface of the heat-resistant material on the one surface of the composite sheet member was 25.64%, and the arithmetic average roughness Ra of that surface was 20.1 ⁇ m.
  • an aqueous dispersion (43 wt.% of hexagonal boron nitride, 2 wt.% of boron oxide, 5 wt.% of boehmite, and 50 wt.% of water) was prepared which was an aqueous dispersion formed with a hexagonal boron nitride powder and a boron oxide powder dispersedly contained in an alumina sol in which boehmite (alumina monohydrate: Al 2 O 3 ⁇ H 2 O) particles as hydrated alumina were dispersedly contained in water (dispersion medium) containing nitric acid, and which exhibited a hydrogen ion concentration (pH) of 2.
  • boehmite alumina monohydrate: Al 2 O 3 ⁇ H 2 O
  • aqueous dispersion 50 wt.% of a lubricating composition containing 86 wt.% of hexagonal boron nitride, 4 wt.% of boron nitride, and 10 wt.% of boehmite was dispersedly contained as a solid content. Further, another aqueous dispersion was prepared in which 50 wt.% of a lubricating composition constituted of a PTFE powder was dispersedly contained as a solid content.
  • aqueous dispersions were mixed to thereby prepare an aqueous dispersion (21.5 wt.% of hexagonal boron nitride, 25 wt.% of PTFE, 1 wt.% of boron oxide, 2.5 wt.% of boehmite, and 50 wt.% of water) in which 50 wt.% of a lubricating composition composed of 43 wt.% of hexagonal boron nitride, 50 wt.% of PTFE, 2 wt.% of boron oxide, and 5 wt.% of boehmite was dispersedly contained as a solid content.
  • a coating operation was repeated three times in which this aqueous dispersion was applied by brush coating to that surface of the aforementioned composite sheet member which was pressurized by the aforementioned roller having the annular recessed grooves and was allowed to dry at a temperature of 100°C.
  • An outer layer forming member was thereby fabricated in which a coating layer (43 wt.% of hexagonal boron nitride, 50 wt.% of PTFE, 2 wt.% of boron oxide, and 5 wt.% of boehmite) of the lubricating composition was formed on the one surface of that composite sheet member.
  • a spherical annular seal member which was comprised of the spherical annular base member having the through hole in its central portion and defined by the cylindrical inner surface, the partially convex spherical surface, and the large- and small-diameter-side annular end faces of the partially convex spherical surface, as well as the outer layer formed integrally on the partially convex spherical surface of the spherical annular base member.
  • the tubular base member was fabricated in the same way as in the above-described Example 14. In this tubular base member, widthwise opposite end portions of the heat-resistant sheet member respectively projected from the reinforcing member in the widthwise direction.
  • a flat composite sheet member was fabricated by using similar materials and a similar method to those of the above-described Example 15. In this composite sheet member, the area ratio of exposure of the surface of the reinforcing member together with the surface of the heat-resistant material on the one surface of the composite sheet member was 23.6%, and the arithmetic average roughness Ra of that surface was 19.7 ⁇ m.
  • an aqueous dispersion (21.5 wt.% of hexagonal boron nitride, 25 wt.% of PTFE, 1 wt.% of boron oxide, 2.5 wt.% of boehmite, and 50 wt.% of water) similar to that of the above-described Example 17 was used.
  • a coating operation was repeated three times in which this aqueous dispersion was applied by brush coating to that surface of the aforementioned composite sheet member which was pressurized by the aforementioned roller having the annular recessed grooves and was allowed to dry at a temperature of 100°C.
  • An outer layer forming member was thereby fabricated in which a coating layer (43 wt.% of hexagonal boron nitride, 50 wt.% of PTFE, 2 wt.% of boron oxide, and 5 wt.% of boehmite) of the lubricating composition was formed on the one surface of that composite sheet member.
  • a coating layer 43 wt.% of hexagonal boron nitride, 50 wt.% of PTFE, 2 wt.% of boron oxide, and 5 wt.% of boehmite
  • a spherical annular seal member which was comprised of the spherical annular base member having the through hole in its central portion and defined by the cylindrical inner surface, the partially convex spherical surface, and the large- and small-diameter-side annular end faces of the partially convex spherical surface, as well as the outer layer formed integrally on the partially convex spherical surface of the spherical annular base member.
  • the tubular base member was fabricated in the same way as in the above-described Example 14. In this tubular base member, widthwise opposite end portions of the heat-resistant sheet member respectively projected from the reinforcing member in the widthwise direction.
  • a flat composite sheet member was fabricated by using similar materials and a similar method to those of the above-described Example 16. In this composite sheet member, the area ratio of exposure of the surface of the reinforcing member together with the surface of the heat-resistant material on the one surface of the composite sheet member was 21.2%, and the arithmetic average roughness Ra of that surface was 10.1 ⁇ m.
  • an aqueous dispersion (21.5 wt.% of hexagonal boron nitride, 25 wt.% of PTFE, 1 wt.% of boron oxide, 2.5 wt.% of boehmite, and 50 wt.% of water) similar to that of the above-described Example 17 was used.
  • a coating operation was repeated three times in which this aqueous dispersion was applied by brush coating to that surface of the aforementioned composite sheet member which was pressurized by the aforementioned roller having the annular recessed grooves and was allowed to dry at a temperature of 100°C.
  • An outer layer forming member was thereby fabricated in which a coating layer (43 wt.% of hexagonal boron nitride, 50 wt.% of PTFE, 2 wt.% of boron oxide, and 5 wt.% of boehmite) of the lubricating composition was formed on the one surface of that composite sheet member.
  • a coating layer 43 wt.% of hexagonal boron nitride, 50 wt.% of PTFE, 2 wt.% of boron oxide, and 5 wt.% of boehmite
  • a spherical annular seal member which was comprised of the spherical annular base member having the through hole in its central portion and defined by the cylindrical inner surface, the partially convex spherical surface, and the large- and small-diameter-side annular end faces of the partially convex spherical surface, as well as the outer layer formed integrally on the partially convex spherical surface of the spherical annular base member.
  • the heat-resistant material for the spherical annular base member As the heat-resistant material for the spherical annular base member, an expanded graphite sheet containing 0.7 wt.% of phosphorus pentoxide, 4.0 wt.% of aluminum primary phosphate, and expanded graphite and having a density of 1.12 Mg/m 3 and a thickness of 0.4 mm was used. After the heat-resistant material was spirally convoluted by a one-circumference portion, the reinforcing member was superposed on the inner side of the heat-resistant material, and the superposed assembly thereof was spirally convoluted, thereby preparing the tubular base member in which the heat-resistant material was located on the outermost periphery. In this tubular base member, widthwise opposite end portions of the heat-resistant material respectively projected from the reinforcing member in the widthwise direction.
  • a heat-resistant material similar to the above-described heat-resistant material was separately prepared, and a coating operation was repeated three times in which an aqueous dispersion (25.5 wt.% of hexagonal boron nitride, 4.5 wt.% of alumina, and 70 wt.% of water), in which 30 wt.% of a lubricating composition composed of 85 wt.% of a hexagonal boron nitride powder and 15 wt.% of an alumina powder was dispersedly contained as a solid content, was applied by brush coating to one surface of that composite sheet member and was allowed to dry at a temperature of 100°C. A coating layer (85 wt.% of hexagonal boron nitride and 15 wt.% of alumina) of the lubricating composition was formed on the one surface of that heat-resistant material.
  • an aqueous dispersion (25.5 wt.% of hexagonal boron nitride, 4.5
  • a belt-shaped metal wire net fabricated by the cylindrical braided metal wire net between rollers was prepared.
  • the heat-resistant material having the aforementioned coating layer was inserted into that belt-shaped metal wire net, and an assembly thereof was passed between rollers so as to be formed integrally, thereby fabricating a composite sheet member in which the lubricating composition and the metal wire net were present on its one surface in mixed form.
  • the area ratio of exposure of the surface of the reinforcing member together with the surface of the heat-resistant material on the one surface of the composite sheet member was 43.42%, and the arithmetic average roughness Ra of that surface was 71.3 ⁇ m.
  • This composite sheet member with its surface where the coating layer of the lubricating composition and the metal wire net were present in mixed form placed on the outer side, was wound around the outer peripheral surface of the aforementioned tubular base member, thereby fabricating the cylindrical preform. Subsequently, this cylindrical preform was subjected to compression forming in a method similar to that of the above-described Example 1, thereby obtaining a spherical annular seal member which was comprised of the spherical annular base member having the through hole in its central portion and defined by the cylindrical inner surface, the partially convex spherical surface, and the large- and small-diameter-side annular end faces of the partially convex spherical surface, as well as the outer layer formed integrally on the partially convex spherical surface of the spherical annular base member.
  • the spherical annular base member was constructed so as to be provided with structural integrity as the heat-resistant material for the spherical annular base member and the reinforcing member for the spherical annular base member made from the metal wire net were compressed and intertwined with each other.
  • the spherical annular base member thus had the reinforcing member for the spherical annular base member made from the compressed metal wire net as well as the heat-resistant material for the spherical annular base member which was constituted of expanded graphite and which filled the meshes of this reinforcing member and was compressed in such a manner as to be formed integrally with this reinforcing member in mixed form.
  • the obverse surface of the outer layer was constituted of a smooth surface of the sliding layer in which the reinforcing member and the lubricating composition of the coating layer were present in mixed form.
  • the tubular base member was fabricated by using similar materials and a similar method to those the above-described Comparative Example 1. In this tubular base member, widthwise opposite end portions of the heat-resistant sheet member respectively projected from the reinforcing member in the widthwise direction.
  • a heat-resistant material similar to that of the above-described Comparative Example 1 was separately prepared, and a coating operation was repeated three times in which an aqueous dispersion (10.2 wt.% of hexagonal boron nitride, 18 wt.% of PTFE, 1.8 wt.% of alumina, and 70 wt.% of water), in which a lubricating composition composed of 85 wt.% of a hexagonal boron nitride powder and 15 wt.% of an alumina powder was set as 100 parts by weight, and 30 wt.% of a lubricating composition (34 wt.% of hexagonal boron nitride, 60 wt.% of PTFE, and 6 wt.% of alumina) dispersedly containing 150 parts by weight of a PTFE powder was dispersedly contained therein as a solid content, was applied by brush coating to one surface of that heat-resistant material and was allowed to dry at
  • a coating layer (34 wt.% of hexagonal boron nitride, 60 wt.% of PTFE, and 6 wt.% of alumina) of the lubricating composition was formed on the one surface of that heat-resistant sheet member.
  • a belt-shaped metal wire net fabricated by the cylindrical braided metal wire net between rollers was prepared.
  • the heat-resistant material having the aforementioned coating layer was inserted into that belt-shaped metal wire net, and an assembly thereof was passed between rollers so as to be formed integrally, thereby fabricating a composite sheet member in which the lubricating composition and the metal wire net were present on its one surface in mixed form.
  • the area ratio of exposure of the surface of the reinforcing member together with the surface of the heat-resistant material on the one surface of the composite sheet member was 45.2%, and the arithmetic average roughness Ra of that surface was 72.6 ⁇ m.
  • the spherical annular base member was constructed so as to be provided with structural integrity as the heat-resistant material for the spherical annular base member and the reinforcing member for the spherical annular base member made from the metal wire net were compressed and intertwined with each other.
  • the spherical annular base member thus had the reinforcing member for the spherical annular base member made from the compressed metal wire net as well as the heat-resistant material for the spherical annular base member which was constituted of expanded graphite and which filled the meshes of this reinforcing member and was compressed in such a manner as to be formed integrally with this reinforcing member in mixed form.
  • the obverse surface of the outer layer was constituted of a smooth surface of the sliding layer in which the heat-resistant material, the reinforcing member, and the lubricating composition were present in mixed form.
  • One exhaust pipe 100 of the exhaust pipe spherical joint shown in Fig. 33 was fixed, and high-temperature gas was circulated into that exhaust pipe 100 to increase the surface temperature of the mating member (flared portion 203 shown in Fig. 33 ) to 300°C.
  • a weight was affixed to the outer peripheral surface of the other exhaust pipe 200, and the exhaust pipe 200 was subjected to oscillating motion ⁇ 0.5° for 120 Hr at a vibrational frequency of 25 Hz, whereupon the surface roughness of the mating member was measured by the ten-point average roughness (Rz JIS).
  • the ambient temperature (the outer surface temperature of the concave spherical surface portion 302 shown in Fig. 33 ) is raised to 500°C while continuing the oscillating motions (the number of oscillating motions during the temperature rise being 45,000).
  • the ambient temperature reached 500°C, 115,000 oscillating motions are performed.
  • the ambient temperature is allowed to drop to room temperature while continuing the oscillating motions (the number of oscillating motions during the temperature drop being 45,000).
  • the combined total of 250,000 oscillating motions is set as one cycle, and four cycles are performed.
  • Tables 1 to 4 show the results of the above-described tests.
  • the surface of the outer layer is constituted of the smooth surface of the sliding layer of the lubricating composition which is integrally adhered to the outer layer intermediate surface of the base layer consisting of the surface of the heat-resistant material for the outer layer and the reinforcing member for the outer layer made flush with the surface of that heat-resistant material as the heat-resistant material for the outer layer and the reinforcing member for the outer layer are press bonded to each other such that the reinforcing member for the outer layer is embedded in the heat-resistant material for the outer layer. Therefore, it is possible to prevent the damaging and coarsening of the surface of the mating member as much as possible in the friction with the mating member, thereby making it possible to prevent a decline in sealability and the generation of abnormal frictional noise.
  • the heat-resistant material for the outer layer constituted of expanded graphite having a lower density than the density of the expanded graphite forming the heat-resistant material for the spherical annular base member is inserted into two layers of the reinforcing member for the outer layer made from the metal wire net, and the reinforcing member for the outer layer with such a heat-resistant material for the outer layer inserted therein is pressurized in the thicknesswise direction of that heat-resistant material and is thereby press bonded to each other, such that the heat-resistant material for the outer layer is densely filled in the meshes of the metal wire net of the reinforcing member for the outer layer, and the reinforcing member for the outer layer is embedded in the heat-resistant material for the outer layer.

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  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Gasket Seals (AREA)
  • Thermal Insulation (AREA)
  • Sealing Devices (AREA)
  • Powder Metallurgy (AREA)
  • Exhaust Silencers (AREA)

Claims (15)

  1. Kugelförmiges ringförmiges Dichtelement (39) zur Verwendung in einer Abgasrohrverbindung, umfassend: ein kugelförmiges ringförmiges Basiselement (37), das von einer zylindrischen Innenfläche (33), einer teilweise konvexen Kugelfläche (34) und groß- und kleindurchmesserseitigen ringförmigen Endflächen (35, 36) der teilweise konvexen Kugelfläche (34) definiert wird; und einer auf der teilweise konvexen Kugelfläche (34) des kugelförmigen ringförmigen Basiselements (37) angefonnten Außenschicht (38),
    wobei das kugelförmige ringförmige Basiselement (37) ein Verstärkungselement (5) aufweist, das aus einem Metalldrahtnetz und einem hitzebeständigen Material (6) gebildet ist, das expandierten Graphit enthält, welches Maschen des Metalldrahtnetzes des Verstärkungselements (5) ausfüllt und derart komprimiert ist, dass es in gemischter Form an dem Verstärkungselement (5) angeformt ist, wobei die Außenschicht (38) eine Basisschicht (46) und eine Gleitschicht (40) umfasst, die aus einer Schmierstoffzusammensetzung besteht und auf der Basisschicht (46) anhaftend an einer Außenschichtzwischenfläche (42) angeformt ist, wobei die Basisschicht (46) ein weiteres Verstärkungselement (15), das aus einem Metalldrahtnetz gebildet und komprimiert ist, und ein weiteres hitzebeständiges Material (14) umfasst, das weiteren expandierten Graphit enthält, welches Maschen des Metalldrahtnetzes des weiteren Verstärkungselements (15) ausfüllt und komprimiert ist, um mit dem weiteren Verstärkungselement (15) pressverbunden zu sein, und zusammen mit einer Oberfläche (41) des weiteren Verstärkungselements (15) die Außenschichtzwischenfläche (42) bildet, wobei die Basisschicht (46) an der teilweise konvexen Kugelfläche (34) angeformt ist dadurch gekennzeichnet,
    dass die Oberfläche (41) des weiteren Verstärkungselements (15) in der Außenschichtzwischenfläche (42) in verteilter Form mit einem Flächenverhältnis von 5 bis 35 % bezogen auf eine Gesamtfläche der Außenschichtzwischenfläche (42) vorliegt, wobei eine Oberfläche (44) der Außenschicht (38) gegenüber einer von einer glatten Fläche (45) der Gleitschicht (40) gebildeten Außenseite freiliegt.
  2. Kugelförmiges ringförmiges Dichtelement (39) nach Anspruch 1, wobei die Schmierstoffzusammensetzung aus einem Polytetrafluorethylenharz besteht.
  3. Kugelförmiges ringförmiges Dichtelement (39) nach Anspruch 1 oder 2, wobei die Schmierstoffzusammensetzung 70 bis 85 Gew.-% hexagonales Bornitrid, 0,1 bis 10 Gew.-% Boroxid und 5 bis 20 Gew.-% Aluminiumhydroxid enthält, wobei die Schmierstoffzusammensetzung wahlweise entweder
    (a) das Polytetrafluorethylenharz in einem Verhältnis von nicht mehr als 300 Gew.-Teilen oder nicht mehr als 200 Gew.-Teilen auf 100 Gew.-Teile der Schmierstoffkomponente enthält oder
    (b) das Polytetrafluorethylenharz in einem Verhältnis von 50 bis 200 Gew.-Teilen oder 50 bis 150 Gew.-Teilen auf 100 Gew.-Teile der Schmierstoffkomponente enthält.
  4. Kugelförmiges ringförmiges Dichtelement (39) nach Anspruch 3, wobei das Aluminiumhydroxid aus Aluminiumoxid-Monohydrat, wie zum Beispiel Böhmit oder Diaspor, Aluminiumoxid-Trihydrat, wie zum Beispiel Gibbsit oder Bayerit, und Pseudoböhmit ausgewählt ist.
  5. Verfahren zur Herstellung des kugelförmigen ringförmigen Dichtelements (39) nach Anspruch 1, das in einer Abgasrohrverbindung verwendet wird und ein kugelförmiges ringförmiges Basiselement (37), das von einer zylindrischen Innenfläche (33), einer teilweise konvexen Kugelfläche (34) und groß- und kleindurchmesserseitigen ringförmigen Endflächen (35, 36) der teilweise konvexen Kugelfläche (34) definiert wird, und eine auf der teilweise konvexen Kugelfläche (34) des kugelförmigen ringförmigen Basiselements (37) angeformte Außenschicht (38) umfasst,
    dadurch gekennzeichnet,
    dass das Verfahren folgende Schritte umfasst:
    (a) Bereitstellen eines aus einer expandierten Graphitfolie mit einer Dichte von α mg/m3 gebildeten hitzebeständigen Materials (6) für das kugelförmige ringförmige Basiselement (37);
    (b) Bereitstellen eines aus einem durch Weben oder Wirken feiner Metalldrähte gewonnenen Metalldrahtnetz gebildeten Verstärkungselements (5) für das kugelförmige ringförmige Basiselement (37), Aufbringen des Verstärkungselements (5) für das kugelförmige ringförmige Basiselement (37) auf das hitzebeständige Material (6) für das kugelförmige ringförmige Basiselement (37) zur Bildung einer Deckanordnung (12) und Einrollen der Deckanordnung (12) zu einer zylindrischen Form zur Bildung eines rohrförmigen Basiselements (13);
    (c) Einfügen eines von einer expandierten Graphitfolie mit einer Dichte von 0,3α bis 0,6α mg/m3 gebildeten hitzebeständigen Materials (14) für die Außenschicht (38) zwischen zwei Schichten eines Verstärkungselements (15) für die Außenschicht (38), das aus einem durch Weben oder Wirken feiner Metalldrähte gewonnenen Metalldrahtnetz gebildet ist, und Beaufschlagen des Verstärkungselements (15) für die Außenschicht (38) mit dem darin eingefügten hitzebeständigen Material (14) für die Außenschicht (38) mit Druck in Richtung der Dicke des hitzebeständigen Materials (14), so dass das hitzebeständige Material (14) für die Außenschicht (38) und das Verstärkungselement (15) für die Außenschicht (38) derart miteinander pressverbunden werden, dass das hitzebeständige Material (14) für die Außenschicht (38) dicht in Maschen des Metalldrahtnetzes des Verstärkungselements (15) für die Außenschicht (38) gefüllt wird und das Verstärkungselement (15) für die Außenschicht (38) in das hitzebeständige Material (14) für die Außenschicht (38) eingebettet wird, wodurch ein flaches Verbundfolienelement (21) ausgebildet wird, in dem eine Oberfläche (52) des hitzebeständigen Materials (14) für die Außenschicht (38) und das Verstärkungselement (15) für die Außenschicht (38) miteinander bündig ausgebildet sind, und das Verstärkungselement (15) für die Außenschicht (38) in einer Oberfläche (41) des Verstärkungselements (15) für die Außenschicht (38) und die Oberfläche (52) des hitzebeständigen Materials (14) für die Außenschicht (38) mit einem Flächenverhältnis von 5 bis 35 % in verteilter Form freiliegen;
    (d) Beschichten einer Oberfläche (51) des Verbundfolienelements (21), an der die Oberfläche (52) des hitzebeständigen Folienelements (14) für die Außenschicht (38) und die Oberfläche (41) des Verstärkungselements (15) für die Außenschicht (38) miteinander bündig ausgebildet sind, mit einer Schmierstoffzusammensetzung zur Bildung eines eine Außenschicht bildenden Elements (23), bei dem eine Deckschicht (22) aus der Schmierstoffzusammensetzung auf dieser Oberfläche (51) ausgebildet ist;
    (e) Wickeln des die Außenschicht bildenden Elements (23) um eine Außenumfangsfläche des rohrförmigen Basiselements (13), wobei die Deckschicht (22) auf einer Außenseite angeordnet wird, zur Bildung einer zylindrischen Vorform (24); und
    (f) Aufsetzen der zylindrischen Vorform (24) auf eine Außenumfangsfläche eines Kerns (28) eines Formwerkzeugs (31)(engl.: die), Platzieren des Kerns (28) in das Formwerkzeug (31) und Druckformen der zylindrischen Vorform (24) in dem Formwerkzeug (31) in einer axialen Richtung des Kerns (28).
  6. Verfahren zur Herstellung des kugelförmigen ringförmigen Dichtelements (39) nach Anspruch 5, wobei das Beaufschlagen des Verstärkungselements (15) für die Außenschicht (38) mit dem darin eingefügten hitzebeständigen Material (14) für die Außenschicht (38) mit Druck in Richtung der Dicke des hitzebeständigen Materials (14) erfolgt, indem selbiges in einen Walzenspalt zwischen einer zylindrischen Walze mit einer glatten Außenumfangsfläche und einer Walze mit einer zylindrischen Außenumfangsfläche mit einer Vielzahl von entlang der axialen Richtung vorgesehenen ringförmigen vertieften Nuten (17) eingeführt wird, und indem selbiges anschließend weiterhin in einen Walzenspalt zwischen einem Paar zylindrischer Walzen (16, 16a, 18, 18a, 19, 20) eingeführt wird, die jeweils eine glatte zylindrische Außenumfangsfläche aufweisen.
  7. Verfahren zur Herstellung des kugelförmigen ringförmigen Dichtelements (39) nach Anspruch 6, wobei die Oberfläche (51) des Verbundfolienelements (21), die mit der Schmierstoffzusammensetzung beschichtet ist und an der die Oberfläche (52) des hitzebeständigen Folienelements (14) für die Außenschicht (38) und die Oberfläche (41) des Verstärkungselements (15) für die Außenschicht (38) miteinander bündig ausgebildet sind, eine Oberfläche (51) des Verbundfolienelements (21) auf einer von der zylindrischen Walze mit den ringförmigen vertieften Nuten (17) mit Druck beaufschlagten Seite ist.
  8. Verfahren zur Herstellung des kugelförmigen ringförmigen Dichtelements (39) nach Anspruch 5, wobei die Beaufschlagung des Verstärkungselements (15) für die Außenschicht (38) mit dem darin eingefügten hitzebeständigen Material (14) für die Außenschicht (38) mit Druck in Richtung der Dicke des hitzebeständigen Materials (14) erfolgt, indem selbiges in einen Walzenspalt zwischen zumindest einem Paar zylindrischer Walzen (16, 16a, 18, 18a, 19, 20) eingeführt wird, die jeweils eine glatte zylindrische Außenumfangsfläche aufweisen.
  9. Verfahren zur Herstellung des kugelförmigen ringförmigen Dichtelements (39) nach einem der Ansprüche 5 bis 8, wobei die Dichte α des hitzebeständigen Materials (6) für das kugelförmige ringförmige Basiselement (37) 1,0 bis 1,5 mg/m3 beträgt.
  10. Verfahren zur Herstellung des kugelförmigen ringförmigen Dichtelements (39) nach einem der Ansprüche 5 bis 9, wobei die Oberflächenrauheit des Verbundfolienelements (21) einen arithmetischen Mittenrauwert Ra von 5 bis 30 µm aufweist.
  11. Kugelförmiges ringförmiges Dichtelement (39) nach einem der Ansprüche 1 bis 4 oder Verfahren zur Herstellung des kugelförmigen ringförmigen Dichtelements (39) nach einem der Ansprüche 5 bis 10, wobei die hitzebeständigen Materialien (6, 14) des kugelförmigen ringförmigen Basiselements (37) und die Außenschicht (38) expandierten Graphit und mindestens eines von 0,05 bis 5,00 Gew.-% Phosphorpentoxid und 1,0 bis 16,0 Gew.-% eines Phosphats enthalten.
  12. Verfahren zur Herstellung des kugelförmigen ringförmigen Dichtelements (39) nach einem der Ansprüche 5 bis 11, wobei die Schmierstoffzusammensetzung, mit der eine Oberfläche (51) des Verbundfolienelements (21) beschichtet ist, eine ein Polytetrafluorethylenharz enthaltende wässrige Dispersion ist.
  13. Verfahren zur Herstellung des kugelförmigen ringförmigen Dichtelements (39) nach einem der Ansprüche 5 bis 11, wobei die Schmierstoffzusammensetzung, mit der eine Oberfläche (51) des Verbundfolienelements (21) beschichtet ist, eine wässrige Dispersion ist, in der ein hexagonales Bornitridpulver und ein Boroxidpulver in dispergierter Form in einem Aluminiumoxid-Sol enthalten sind, in dem Aluminiumhydroxid-Partikel in dispergierter Form in Wasser enthalten sind, das eine Säure als Dispersionsmedium enthält, und das eine Wasserstoffionenkonzentration von 2 bis 3 aufweist, wobei die wässrige Dispersion als Feststoffanteil 70 bis 85 Gew.-% hexagonales Bornitrid, 0,1 bis 10 Gew.-% Boroxid und 5 bis 20 Gew.-% Aluminiumhydroxid enthält, wobei wahlweise entweder
    (a) ein Polytetrafluorethylenharz in einem Verhältnis von nicht mehr als 300 Gew.-Teilen oder nicht mehr als 200 Gew.-Teilen auf 100 Gew.-Teile der Schmierstoffzusammensetzungskomponente enthalten ist oder
    (b) ein Polytetrafluorethylenharz in einem Verhältnis von 50 bis 200 Gew.-Teilen oder 50 bis 150 Gew.-Teilen auf 100 Gew.-Teile der Schmierstoffzusammensetzungskomponente enthalten ist.
  14. Verfahren zur Herstellung des kugelförmigen ringförmigen Dichtelements (39) nach Anspruch 13, wobei die als Dispersionsmedium in dem Wasser enthaltene Säure Salpetersäure ist und/oder wobei das Aluminiumhydroxid aus Aluminiumoxid-Monohydrat, wie zum Beispiel Böhmit oder Diaspor, Aluminiumoxid-Trihydrat, wie zum Beispiel Gibbsit oder Bayerit, und Pseudoböhmit ausgewählt ist.
  15. Verfahren zur Herstellung des kugelförmigen ringförmigen Dichtelements (39) nach einem der Ansprüche 5 bis 14, wobei die Dichte des hitzebeständigen Folienelements (14) für die Außenschicht (38) 0,3 bis 0,9 mg/m3 beträgt.
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JP4953222B2 (ja) 2005-05-20 2012-06-13 本田技研工業株式会社 球帯状シール体
JP5347970B2 (ja) * 2007-12-05 2013-11-20 オイレス工業株式会社 球帯状シール体及びその製造方法

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BRPI0822081A2 (pt) 2015-06-23
CN101903690B (zh) 2013-10-30
BRPI0822081B1 (pt) 2020-03-31
CN101903690A (zh) 2010-12-01
US8567793B2 (en) 2013-10-29
JPWO2009078165A1 (ja) 2011-04-28
WO2009078165A1 (ja) 2009-06-25
JP5347971B2 (ja) 2013-11-20
RU2010124638A (ru) 2012-01-27
EP2243987A4 (de) 2013-07-17
RU2451224C2 (ru) 2012-05-20
EP2243987A1 (de) 2010-10-27

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